Dyes and dye-donor elements for use in thermal dye sublimation transfer

ABSTRACT

Dye corresponding to the following formula - ##STR1## wherein Z represents CN, COOR 1  or CONR 2  R 3  ; 
     R 1 , R 2  and R 3  each independently represents hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, or R 2  and R 3  together represent the necessary atoms to close a heterocyclic nucleus or substituted heterocyclic nucleus; 
     Y represents OR 4  or NR 5  R 6  or CN; 
     R 4  represents hydrogen, substituted or unsubstituted or unsubstituted aryl, SO 2  R 7 , COR 7 , CSR 7 , POR 7  R 8  ; 
     R 5  and R 6  each independently has one of the significances given to R 4  or represents substituted or unsubstituted amino, or R 5  and R 6  together represent the necessary atoms to close a heterocyclic nucleus or substituted heterocyclic nucleus, including a heterocyclic nucleus with an aliphatic or aromatic ring fused-on; 
     R 7  and R 8  each independently represents substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkyloxy, substituted or unsubstituted arloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted amino or a substituted or unsubstituted heterocyclic group or R 7  and R 8  together represent the necessary atoms to close a 5- or 6-membered ring; 
     X represents N-Ar; 
     Ar represents an aromatic nucleus substituted in para position by a substituent chosen from the group consisting of substituted or unsubstituted amino, substituted or unsubstituted alkyloxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, hydroxy and mercapto.

This is a division of application Ser. No. 07/524,461 filed May 17,1990, now U.S. Pat. No. 5,026,677.

DESCRIPTION

The present invention relates to dye-donor elements for use according tothermal dye sublimation transfer and to novel dyes for use in saiddye-donor elements.

Thermal dye sublimation transfer is a recording method in which adye-donor element provided with a dye layer containing sublimable dyeshaving heat transferability is brought into contact with a receiversheet and selectively, in accordance with a pattern information signal,heated with a thermal printing head provided with a plurality ofjuxtaposed heat-generating resistors, whereby dye from the selectivelyheated regions of the dye-donor element is transferred to the receiversheet and forms a pattern thereon, the shape and density of which is inaccordance with the pattern and intensity of heat applied to thedye-donor element.

A dye-donor element for use according to thermal dye sublimationtransfer usually comprises a very thin support e.g. a polyester support,one side of which is covered with a dye layer, which contains theprinting dyes. Usually an adhesive or subbing layer is provided betweenthe support and the dye layer. Normally the opposite side is coveredwith a slipping layer that provides a lubricated surface against whichthe thermal printing head can pass without suffering abrasion. Anadhesive layer may be provided between the support and the slippinglayer.

The dye layer can be a monochrome dye layer or it may comprisesequential repeating areas of different dyes like e.g. cyan, magenta andyellow dyes. When a dye-donor element containing three or more primarycolor dyes is used, a multicolor image can be obtained by sequentiallyperforming the dye transfer process steps for each color.

Any dye can be used in such a dye layer provided it is easilytransferable to the dye-image-receiving layer of the receiver sheet bythe action of heat.

Typical and specific examples of dyes for use in thermal dye sublimationtransfer have been described in, e.g., EP 209990, EP 209991, EP 216483,EP 218397, EP 227095, EP 227096, EP 229374, EP 235939, EP 247737, EP257577, EP 257580, EP 258856, EP 279330, EP 279467, EP 285665, U.S. Pat.Nos. 4,743,582, 4,753,922, 4,753,923, 4,757,046, 4,769,360, 4,771,035,JP 84/78894, JP 84/78895, JP 84/78896, JP 84/227490, JP 84/227948, JP85/27594, JP 85/30391, JP 85/229787, JP 85/229789, JP 85/229790, JP85/229791, JP 85/229792, JP 85/229793, JP 85/229795, JP 86/41596, JP86/268493, JP 86/268494, JP 86/268495 and JP 86/284489.

It is an object of the present invention to provide novel dye-donorelements for use according to thermal dye sublimation transfer printing.

It is another object of the present invention to provide novel dyeswhich may be used in said dye-donor elements.

Other objects will become apparent from the description hereinafter.

In accordance with the present invention a dye-donor element for useaccording to thermal dye sublimation transfer is provided, saiddye-donor element comprising a support having thereon a dye layercontaining a dye characterized in that said dye corresponds to thefollowing formula ##STR2## wherein Z represents CN, COOR¹ or CONR² R³ ;

R¹, R² and R³ each independently represent hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, or R² and R³ together represent thenecessary atoms to close a heterocyclic nucleus or substitutedheterocyclic nucleus;

Y represents OR⁴ or NR⁵ R⁶ or CN;

R⁴ represents hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted cycloalkyl, substituted or unsubstituted aryl, SO₂ R⁷,COR⁷, CSR⁷, POR⁷ R⁸ ;

R⁵ and R⁶ each independently has one of the significances given to R⁴ orrepresent substituted or unsubstituted amino, or R⁵ and R⁶ togetherrepresent the necessary atoms to close a heterocyclic nucleus orsubstituted heterocyclic nucleus, including a heterocyclic nucleus withan aliphatic or aromatic ring fused-on;

R⁷ and R⁸ each independently represent substituted or unsubstitutedalkyl, substituted or unsubstituted cycloalkyl, substituted orunsubstituted alkenyl, substituted or unsubstituted aralkyl, substitutedor unsubstituted aryl, substituted or unsubstituted alkyloxy,substituted or unsubstituted aryloxy, substituted or unsubstitutedalkylthio, substituted or unsubstituted arylthio, substituted orunsubstituted amino or a substituted or unsubstituted heterocyclic groupor R⁷ and R⁸ together represent the necessary atoms to close a 5- or 6-membered ring;

X represents N-Ar, N-Het, CR⁹ R¹⁰, N-NR¹¹ R¹² or N--N═CR¹³ R¹⁴ ;

Ar represents an aromatic nucleus substituted in para position by asubstitutent chosen from the group consisting of substituted orunsubstituted amino, substituted or unsubstituted alkyloxy, substitutedor unsubstituted aryloxy, substituted or unsubstituted alkylthio,substituted or unsubstituted arylthio, hydroxy, mercapto;

Het represents a substituted or unsubstituted heterocyclic ring;

R⁹ and R¹⁰ each independently represents hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, substituted or unsubstituted alkenyl,substituted or unsubstituted alkynyl, a substituted or unsubstitutedheterocyclic ring, cyano, halogen, SO₂ R⁷, COR⁷, CSR⁷, POR⁷ R⁸ or R⁹ andR¹⁰ together represent the necessary atoms to close a substituted orunsubstituted ring including a substituted or unsubstituted heterocyclicring;

R¹¹ represents a substituted or unsubstituted aromatic ring, including asubstituted or unsubstituted aromatic heterocyclic ring;

R¹² has one of the significances given to R⁴ and

R¹³ and R¹⁴ each independently represent hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, or R¹³ and R¹⁴ together represent thenecessary atoms to close a substituted or unsubstituted heterocyclicnucleus, including a heterocyclic nucleus with an aliphatic or aromaticring fused-on.

According to a special embodiment of this invention wherein X representsN-Ar, the dyes correspond to general formula (I) ##STR3## wherein Z andY are defined as hereinbefore;

R¹⁵, R¹⁶, R¹⁸ and R¹⁹ each independently represent hydrogen, substitutedor unsubstituted alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, substituted or unsubstitutedalkyloxy, substituted or unsubstituted aryloxy, substituted orunsubstituted carbonamido, substituted or unsubstituted sulfamido,hydroxy, halogen, NH--SO₂ R⁷, NH--COR⁷, O--SO₂ R⁷, O--COR⁷, R⁷ being asdefined hereinbefore, or R¹⁵ and R¹⁶ together and/or R¹⁸ and R¹⁹together represent the necessary atoms to close (a) substituted orunsubstituted ring(s) fused-on the benzene ring or R¹⁶ and/or R¹⁸together with R²¹ and/or R²² represent the necessary atoms to close asubstituted or unsubstituted heterocyclic ring fused-on the benzenering;

R¹⁷ represents OR²⁰, SR²⁰ or NR²¹ R²² ;

R²⁰ represents hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted cycloakyl, substituted or unsubstituted aryl and

R²¹ and R²² each independently has one of the significances given to R²⁰or represent a substituted or unsubstituted heterocyclic group or R²¹and R²² together represent the necessary atoms to close a substituted orunsubstituted heterocyclic ring or R²¹ and/or R²² together with R¹⁶and/or R¹⁸ represent the necessary atoms to close a substituted orunsubstituted heterocyclic ring fused-on the benzene ring.

Hereinafter * represents the linking position.

Representative examples of dyes according to formula (I) are listedbelow in table 1.

                                      TABLE 1                                     __________________________________________________________________________    Z     Y              R.sup.15 R.sup.16                                                                         R.sup.17       R.sup.18                                                                         R.sup.19                                                                         no.                     __________________________________________________________________________    CN    N(CH.sub.2 C.sub.6 H.sub.5).sub.2                                                            H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.1                     CN                                                                                   ##STR4##      CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.2                     CN    OCH.sub.3      CH.sub.3 CH.sub.3                                                                         N(C.sub.2 H.sub.5).sub.2                                                                     CH.sub.3                                                                         CH.sub.3                                                                         I.3                     CN    NHSO.sub.2 C.sub.6 H.sub.4 CH.sub.3                                                          CH.sub.3 H                                                                                 ##STR5##      H  H  I.4                     CN                                                                                   ##STR6##      CH.sub.3 H                                                                                 ##STR7##      H  H  I.5                     CN                                                                                   ##STR8##      NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.6                     CN                                                                                   ##STR9##      H        H                                                                                 ##STR10##     H  H  I.7                     CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  CH.sub.3 H                                                                                 ##STR11##     H  H  I.8                     COOCH.sub.3                                                                          ##STR12##     CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  CH.sub.3                                                                         I.9                     COOC.sub.2 H.sub.5                                                                   ##STR13##     H        H  N(C.sub.4 H.sub.9).sub.2                                                                     H  H  I.10                    CN    OSO.sub.2 N(CH.sub.3).sub.2                                                                  H        H  N(C.sub.3 H.sub.7).sub.2                                                                     H  H  I.11                    CN    NHCOCHCH.sub.2 H        H                                                                                 ##STR14##     H  H  I.12                    CN    NH.sub.2       NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.13                    CN    OCH.sub.2 C.sub.6 H.sub.5                                                                    H                                                                                          ##STR15##        H  I.14                    CN                                                                                   ##STR16##     H                                                                                          ##STR17##     H  H  I.15                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.16                    CN    CN             NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.17                    CN    NHCOC(CH.sub.3)CH.sub.2                                                                      CH.sub.3 CH.sub.3                                                                         N(C.sub.2 H.sub.5 ).sub.2                                                                    CH.sub.3                                                                         CH.sub.3                                                                         I.18                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  CH.sub.3 H                                                                                 ##STR18##     H  H  I.19                    CN                                                                                   ##STR19##     CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.20                    CN                                                                                   ##STR20##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.21                    CN                                                                                   ##STR21##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.22                    CN    NHCOOCH.sub.3  H        H                                                                                 ##STR22##     H  H  I.23                    CN                                                                                   ##STR23##     CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  CH.sub.3                                                                         I.24                    CN    NH.sub.2       NHCOCH(CH.sub.3).sub.2                                                                 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.25                    CN    NH.sub.2       H        H  N(C.sub.3 H.sub.7).sub.2                                                                     H  H  I.26                    CN    NHCOC.sub.6 H.sub.5                                                                          H        H                                                                                 ##STR24##     H  H  I.27                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.28                    CN    N(CH.sub.3).sub.2                                                                            H                                                                                          ##STR25##        H  I.29                    CN    NHSO.sub.2 CH.sub.3                                                                          H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.30                    CN    NH.sub.2       N(SO.sub.2 CH.sub.3).sub.2                                                             H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.31                    CN    NH.sub.2       CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.32                    CN    OCH(CH.sub.3).sub.2                                                                          CH.sub.3 CH.sub.3                                                                         N(C.sub.2 H.sub.5).sub.2                                                                     CH.sub.3                                                                         CH.sub.3                                                                         I.33                    CN                                                                                   ##STR26##     CH.sub.3 H                                                                                 ##STR27##     H  H  I.34                    CN                                                                                   ##STR28##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.35                    CN    N(COOC.sub.16 H.sub.33).sub.2                                                                NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.36                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  H                                                                                          ##STR29##        H  I.37                    CN                                                                                   ##STR30##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.38                    CN    NHCOOC.sub.4 H.sub.9                                                                         CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  CH.sub.3                                                                         I.39                    CN    NHCOC.sub.2 H.sub.5                                                                          H        H  N(C.sub.4 H.sub.9).sub.2                                                                     H  H  I.40                    CN    OC.sub.6 H.sub.4 CH.sub.3                                                                    H        H  N(C.sub.3 H.sub.7).sub.2                                                                     H  H  I.41                    CN    NH.sub.2       H        H                                                                                 ##STR31##     H  H  I.42                    CN    OC(CH.sub.3).sub.3                                                                           NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.43                    CN    NHSO.sub.2 C.sub.6 H.sub.5                                                                   H                                                                                          ##STR32##        H  I.44                    CN    NHCOOC(CH.sub.3).sub.3                                                                       H                                                                                          ##STR33##     H  H  I.45                    CN    NH.sub.2       NHCOC.sub.5 H.sub.11                                                                   H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.46                    CN    OCOCH.sub.3    CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.47                    CN    N(C.sub.3 H.sub.7).sub.2                                                                     CH.sub.3 CH.sub.3                                                                         N(C.sub.2 H.sub.5).sub.2                                                                     CH.sub.3                                                                         CH.sub.3                                                                         I.48                    CN    NH.sub.2       CH.sub.3 H                                                                                 ##STR34##     H  H  I.49                    CN    NHCOCH.sub.3   CH.sub.3 H                                                                                 ##STR35##     H  H  I.50                    CN    NH.sub.2       H        H  N(C.sub.2 H.sub.4 OH).sub.2                                                                  H  H  I.51                    CN                                                                                   ##STR36##     H                                                                                          ##STR37##        H  I.52                    CN                                                                                   ##STR38##     H        H  N(C.sub.4 H.sub.9).sub.2                                                                     H  H  I.53                    CN    NHCOOCH.sub.2 C.sub.6 H.sub.5                                                                CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  CH.sub.3                                                                         I.54                    CN    N(PO(OC.sub.6 H.sub.5).sub.2).sub.2                                                          H        H  N(C.sub.4 H.sub.9).sub.2                                                                     H  H  I.55                    COOCH.sub.3                                                                         NHCOCHCH.sub.2 H        H  N(C.sub.3 H.sub.7).sub.2                                                                     H  H  I.56                    CN    OCOC.sub.3 H.sub.7                                                                           H        H                                                                                 ##STR39##     H  H  I.57                    COOC.sub.2 H.sub.5                                                                  N(COOC.sub.4 H.sub.9).sub.2                                                                  NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.58                    COOCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                            H                                                                                          ##STR40##        H  I.59                    CN    N(COOCH.sub.3).sub.2                                                                         H                                                                                          ##STR41##     H  H  I.60                    CN    NH.sub.2       H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.61                    CN    NH.sub.2       NHCOC.sub.7 H.sub.15                                                                   H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.62                    CN    NHPO(OC.sub.6 H.sub.5).sub.2                                                                 CH.sub.3 CH.sub.3                                                                         N(C.sub.2 H.sub.5).sub.2                                                                     CH.sub.3                                                                         CH.sub.3                                                                         I.63                    CN    NH.sub.2       H        H                                                                                 ##STR42##     H  H  I.64                    CN    N(COOC.sub.4 H.sub.9).sub.2                                                                  H        H                                                                                 ##STR43##     H  H  I.65                    COOC.sub.2 H.sub.5                                                                  N(C.sub.2 H.sub.4 OH).sub.2                                                                  H        H  N(C.sub.2 H.sub.4 OH).sub.2                                                                  H  H  I.66                    COOCH.sub.3                                                                         NHCOOCH.sub.3  H        H                                                                                 ##STR44##     H  H  I.67                    CN                                                                                   ##STR45##     H        H                                                                                 ##STR46##     H  H  I.68                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  CH.sub.3                                                                         I.69                    CN    NH.sub.2       CH(CH.sub.3).sub.2                                                                     H  N(CH.sub.3).sub.2                                                                            H  H  I.70                    COOCH.sub.3                                                                         OH             H        H  N(C.sub.3 H.sub.7).sub.2                                                                     H  H  I.71                    COOC.sub.2 H.sub.5                                                                  NHCOOCH.sub.2 C.sub.6 H.sub.5                                                                H        H                                                                                 ##STR47##     H  H  I.72                    CN    NHC.sub.6 H.sub.5                                                                            NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.73                    CN    N(COOC.sub.4 H.sub.9).sub.2                                                                  H                                                                                          ##STR48##        H  I.74                    CN    OCOC.sub.15 H.sub.31                                                                         H                                                                                          ##STR49##     H  H  I.75                    CN                                                                                   ##STR50##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.76                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.77                    COOC.sub.2 H.sub.5                                                                   ##STR51##     CH.sub.3 CH.sub.3                                                                         N(C.sub.2 H.sub.5).sub.2                                                                     CH.sub.3                                                                         CH.sub.3                                                                         I.78                    CN    OSO.sub.2 C.sub.6 H.sub.5                                                                    CH.sub.3 H                                                                                 ##STR52##     H  H  I.79                    COOCH.sub.3                                                                         NHCOC.sub.2 H.sub.5                                                                          CH.sub.3 H                                                                                 ##STR53##     H  H  I.80                    CN    NHSO.sub.2 C.sub.6 H.sub.4 NHCOCH.sub.3                                                      H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.81                    CN    NH.sub.2       H        H                                                                                 ##STR54##     H  H  I.82                    CN                                                                                   ##STR55##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.83                    CN    N(COOC(CH.sub.3).sub.3).sub.2                                                                CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  CH.sub.3                                                                         I.84                    CN    NH.sub.2       H        H  N(C.sub.4 H.sub.9).sub.2                                                                     H  H  I.85                    CN    OSO.sub.2 C.sub.6 H.sub.4 CH.sub.3                                                           H        H  N(C.sub.3 H.sub.7).sub.2                                                                     H  H  I.86                    CN    NHC.sub.2 H.sub.4 OH                                                                         H        H                                                                                 ##STR56##     H  H  I.87                    COOCH.sub.3                                                                         NHSO.sub.2 CH.sub.3                                                                          NHCOCH.sub. 3                                                                          H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.88                    COOC.sub.2 H.sub.5                                                                  NHCOOC(CH.sub.3).sub.3                                                                       H                                                                                          ##STR57##        H  I.89                    CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                         H                                                                                          ##STR58##     H  H  I.90                    CN                                                                                   ##STR59##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.91                    CN    N(COOC.sub.4 H.sub.9).sub.2                                                                  NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.                                                                      H  H  I.92                    CN    N(COOC.sub.4 H.sub.9).sub.2                                                                  NHCOC.sub.5 H.sub.11                                                                   H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.93                    CN                                                                                   ##STR60##     NHCOC.sub.5 H.sub.11                                                                   H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.94                    CN                                                                                   ##STR61##     NHCOC.sub.5 H.sub.11                                                                   H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.95                    CN    N(COOCH.sub.2 CH(CH.sub.3).sub.2).sub.2                                                      NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.96                    CN    NH.sub.2       H                                                                                          ##STR62##        H  I.97                    CN                                                                                   ##STR63##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.98                    CN                                                                                   ##STR64##     CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  CH.sub.3                                                                         I.99                    CN    N(COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCO).sub.2                                             H        H  N(C.sub.4 H.sub.9).sub.2                                                                     H  H  I.100                   COOCH.sub.3                                                                         NHCOC.sub.6 H.sub.5                                                                          H        H  N(C.sub.3 H.sub.7).sub.2                                                                     H  H  I.101                   COOC.sub.2 H.sub.5                                                                   ##STR65##     H        H                                                                                 ##STR66##     H  H  I.102                   CN    NHCOOC.sub.4 H.sub.9                                                                         NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.103                   CN    N(C.sub.2 H.sub.4 OH).sub.2                                                                  H                                                                                          ##STR67##        H  I.104                   CN    N(COO(C.sub.2 H.sub.4 O).sub.3 CO).sub.2                                                     H                                                                                          ##STR68##     H  H  I.105                   CN                                                                                   ##STR69##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.106                   CN    N(COOCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9).sub.2                                      NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.107                   CN                                                                                   ##STR70##     NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.108                   CN                                                                                   ##STR71##     H        H                                                                                 ##STR72##     H  H  I.109                   CN                                                                                   ##STR73##     CH.sub.3 H                                                                                 ##STR74##     H  H  I.110                   CN    N(COOC.sub.4 H.sub.9).sub.2                                                                  NHCOCH(CH.sub.3).sub.2                                                                 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.111                   CN    NH.sub.2       CH.sub.3                                                                                   ##STR75##        H  I.112                   CN                                                                                   ##STR76##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.113                   CN                                                                                   ##STR77##     N(SO.sub.2 CH.sub.3).sub.2                                                             H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.114                   CN                                                                                   ##STR78##     H        H                                                                                 ##STR79##     H  H  I.115                   CN                                                                                   ##STR80##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.116                   CN                                                                                   ##STR81##     NHCOC.sub.5 H.sub.11                                                                   H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.117                   COOC.sub.2 H.sub.5                                                                  NH.sub.2       NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.118                   CN                                                                                   ##STR82##     CH.sub.3                                                                                   ##STR83##        H  I.119                   COOCH.sub.3                                                                         NHCOC.sub.4 H.sub.9                                                                          H                                                                                          ##STR84##     H  H  I.120                   CN    NH.sub.2       H        H                                                                                 ##STR85##     H  H  I.121                   CN    NH.sub.2       OC.sub.2 H.sub.5                                                                       H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.122                   CN    N(COCH.sub.3).sub.2                                                                          H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.123                   CN                                                                                   ##STR86##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  1.124                   CN                                                                                   ##STR87##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.125                   CN                                                                                   ##STR88##     H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.126                   CN                                                                                   ##STR89##     CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.127                   CN                                                                                   ##STR90##     CH.sub.3 H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.128                   CN    NHCOOC.sub.2 H.sub.5                                                                         H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.129                   CN                                                                                   ##STR91##     NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.130                   CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.131                   CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                         NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.132                   CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                         H        H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.133                   CN                                                                                   ##STR92##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.134                   CN                                                                                   ##STR93##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.135                   CN                                                                                   ##STR94##     NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.136                   CN                                                                                   ##STR95##     NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.137                   CN                                                                                   ##STR96##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.138                   CN                                                                                   ##STR97##     NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.139                   CN    NH.sub.2       NHCOC(CH.sub.3).sub.3                                                                  H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.140                   CN    NH.sub.2       OC.sub.2 H.sub.5                                                                       H  N(C.sub.4 H.sub.9).sub.2                                                                     H  H  I.141                   CN                                                                                   ##STR98##     NHCOCH.sub.3                                                                           H  N(C.sub.2 H.sub.5).sub.2                                                                     H  H  I.142                   CN                                                                                   ##STR99##     NHCOCH.sub.3                                                                               ##STR100##       H  I.143                   __________________________________________________________________________

Dyes according to formula (I) can be obtained by oxidative couplingbetween a malononitrile dimer and a p-phenylenediamine compound or bycondensation of a malononitrile dimer and a nitrosoaryl compound.

The synthesis of malononitrile dimers is described by A. J. Fatiadi inSynthesis, 1978, pages 165 to 204 and by F. Freeman in Chemical Reviews,Vol. 69, 1969, pages 519 to 624.

The synthesis of dyes according to formula (I) wherein Y represents NH₂is described by H. Junek, B. Thierrichter and P. Wibmer in Monatsheftefur Chemie, Vol. 110, 1979, pages 483 to 492 and in U.S. Pat. No.2,926,187. Dyes according to formula (I) wherein Y is not NH₂ have notbeen described before.

Among the dyes according to formula (I) those wherein Z is CN and Y isNR⁵ R⁶ are preferred; and among those the dyes wherein R¹⁷ is NR²¹ R²²are preferred.

The dyes according to the present invention wherein X represents CR⁹R¹⁰, can be represented by the following formula (II) ##STR101## whereinZ, Y, R⁹ and R¹⁰ are defined as hereinbefore.

In a particular type of dye according to formula (II), R⁹ and R¹⁰together with the C atom to which they are attached represent thenecessary atoms to close a pyrone-type nucleus represented by ##STR102##wherein V represents O, S, Se, Te, NR²⁷, preferably O or NR²⁷ ;

R²³, R²⁴, R²⁵ and R²⁶ each independently represent hydrogen, substitutedor unsubstituted alkyl, substituted or unsubstituted alkenyl,substituted or unsubstituted cycloalkyl, substituted or unsubstitutedaryl, alkyloxycarbonyl, aryloxycarbonyl, substituted or unsubstitutedcarbonamido, or R²³ and R²⁴ together and/or R²⁵ and R²⁶ togetherrepresent the necessary atoms to close (a) substituted or unsubstitutedring(s) fused-on the pyrone-type nucleus and

R²⁷ represents hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted cycloalkyl, substituted or unsubstituted aryl or amino.

Representative examples of dyes according to formula (II) are listedbelow in table 2.

                                      TABLE 2                                     __________________________________________________________________________    Z     Y              R.sup.9             R.sup.10                                                                             no.                           __________________________________________________________________________    COOCH.sub.3                                                                         OCOC(CH.sub.3).sub.3                                                                         COC.sub.6 H.sub.5   C.sub.6 H.sub.5                                                                      II.1                          CN    NHCOOC(CH.sub.3).sub.3                                                                       COC.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                               C.sub.6 H.sub.5                                                                      II.2                          CN                                                                                   ##STR103##    COC.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                        C.sub.6 H.sub.5                                                                      II.3                          CN    NH.sub.2                                                                                      ##STR104##         H      II.4                          CN                                                                                   ##STR105##                                                                                   ##STR106##         H      II.5                          CN    NH.sub.2       C.sub.6 H.sub.4 N(CH.sub.3).sub. 2                                                                H      II.6                          CN    NH.sub.2       C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                          H      II.7                          CN    NH.sub.2                                                                                      ##STR107##         H      II.8                          CN    NH.sub.2       CHCHC.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                             H      II.9                          CN                                                                                   ##STR108##    CHCHC.sub.6 H.sub.4N(CH.sub.3).sub.2                                                              H      II.10                         CN                                                                                   ##STR109##                                                                                   ##STR110##         CN     II.11                         CN    NHCOCH.sub.3                                                                                  ##STR111##         H      II.12                         CN                                                                                   ##STR112##                                                                                   ##STR113##                II.13                         CN                                                                                   ##STR114##                                                                                   ##STR115##                II.14                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR116##                II.15                         COOCH.sub.3                                                                         N(COOCH.sub.3).sub.2                                                                          ##STR117##         H      II.16                         CN    NH.sub.2                                                                                      ##STR118##         H      II.17                         CN                                                                                   ##STR119##                                                                                   ##STR120##                II.18                         CN                                                                                   ##STR121##                                                                                   ##STR122##                II.19                         CN                                                                                   ##STR123##                                                                                   ##STR124##                II.20                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR125##                II.21                         CN                                                                                   ##STR126##                                                                                   ##STR127##                II.22                         CN                                                                                   ##STR128##                                                                                   ##STR129##         H      II.23                         CN    NH.sub.2       C.sub.6 H.sub.4 OCH.sub.3                                                                         H      II.24                         COOC.sub.2 H.sub.5                                                                  N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR130##         H      II.25                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR131##         H      II.26                         CN    N(COOC.sub.16 H.sub.33).sub.2                                                                 ##STR132##                II.27                         CN                                                                                   ##STR133##                                                                                   ##STR134##                II.28                         COOC.sub.2 H.sub.5                                                                  NHSO.sub.2 C.sub.6 H.sub.5                                                                    ##STR135##         H      II.29                         CN    NH.sub.2       C.sub.6 H.sub.4 N(CH.sub.2 COOCH.sub.3).sub.2                                                     H      II.30                         CN    OSO.sub.2 CH.sub.3                                                                            ##STR136##         H      II.31                         CN    N(COOCH.sub.3).sub.2                                                                          ##STR137##         H      II.32                         CN    NHCH.sub.2 CH(CH.sub.3).sub.2                                                                 ##STR138##         H      II.33                         CN                                                                                   ##STR139##                                                                                   ##STR140##         H      II.34                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  CHCHC.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                             H      II.35                         CN    N(COOC.sub.4 H.sub.9).sub.2                                                                   ##STR141##                II.36                         CN                                                                                   ##STR142##                                                                                   ##STR143##                II.37                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR144##                II.38                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR145##                II.39                         CN                                                                                   ##STR146##                                                                                   ##STR147##                II.40                         CN                                                                                   ##STR148##                                                                                   ##STR149##                II.41                         CN                                                                                   ##STR150##    COC.sub.6 H.sub.5   C.sub.6 H.sub.5                                                                      II.42                         CN                                                                                   ##STR151##    COC.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                               C.sub.6 H.sub.5                                                                      II.43                         CN    N(COOC(CH.sub.3).sub.3).sub.2                                                                COC.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                        C.sub.6 H.sub.5                                                                      II.44                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                          H      II.45                         CN                                                                                   ##STR152##    COC.sub.6 H.sub.4 N(CH.sub. 3).sub.2                                                              C.sub.6 H.sub.4 N(CH.sub.3).sub.2                                             7      II.46                         COOCH.sub.3                                                                         NH(C.sub.2 H.sub.4 OH).sub.2                                                                 C.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                                 H      II.47                         COOCH.sub.3                                                                          ##STR153##    C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                          H      II.48                         COOC.sub.2 H.sub.5                                                                  N(COOC.sub.4 H.sub.9).sub.2                                                                   ##STR154##         H      II.49                         CN                                                                                   ##STR155##                                                                                   ##STR156##                II.50                         CN                                                                                   ##STR157##                                                                                   ##STR158##         CN     II.51                         CN                                                                                   ##STR159##                                                                                   ##STR160##         H      II.52                         CN    OH                                                                                            ##STR161##         H      II.53                         COOCH.sub.3                                                                          ##STR162##                                                                                   ##STR163##         H      II.54                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR164##                II.55                         COOC.sub.2 H.sub.5                                                                  OH                                                                                            ##STR165##         H      II.56                         CN    NHPO(OC.sub.6 H.sub.5).sub.2                                                                  ##STR166##         H      II.57                         COOCH.sub.3                                                                         NHSO.sub.2 CH.sub.3                                                                          C.sub.6 H.sub.4 N(C.sub.6 H.sub.5).sub.2                                                          H      II.58                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR167##         H      II.59                         CN                                                                                   ##STR168##    C.sub.6 H.sub.4 OCH.sub.3                                                                         H      II.60                         CN    N(COOCH.sub.2 CH(CH.sub.3).sub.2).sub.2                                                       ##STR169##         H      II.61                         CN    OC(CH.sub.3).sub.3                                                                            ##STR170##         H      II.62                         CN    NH.sub.2                                                                                      ##STR171##         H      II.63                         CN                                                                                   ##STR172##                                                                                   ##STR173##         H      II.64                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  C.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                                 H      II.65                         CN    OCH.sub.3                                                                                     ##STR174##         H      II.66                         CN    NH.sub.2                                                                                      ##STR175##         H      II.67                         CN    NHCOC(CH.sub.3)CH.sub.2                                                                       ##STR176##         H      II.68                         CN    OSO.sub.2 CH.sub.3                                                                            ##STR177##         H      II.69                         CN    N(COOCH.sub.2 CH(CH.sub.3 ).sub.2).sub.2                                                     C.sub.6 H.sub.4 N(CH.sub.2 COOCH.sub.3).sub.2                                                     H      II.70                         CN    NH.sub.2                                                                                      ##STR178##         H      II.71                         CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                          ##STR179##                II.72                         CN                                                                                   ##STR180##                                                                                   ##STR181##                II.73                         CN                                                                                   ##STR182##                                                                                   ##STR183##                II.74                         CN    NH.sub.2                                                                                      ##STR184##                II.75                         CN                                                                                   ##STR185##                                                                                   ##STR186##                II.76                         CN    NH.sub.2       COC.sub.6 H.sub.5   C.sub.6 H.sub.5                                                                      II.77                         CN                                                                                   ##STR187##    COC.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                               C.sub.6 H.sub.5                                                                      II.78                         CN    NHSO.sub.2 C.sub.6 H.sub.4 CH.sub.3                                                          COC.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                        C.sub.6 H.sub.5                                                                      II.79                         CN    N(COOC.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCO).sub.2                                             COC.sub.6 H.sub.4 Cl                                                                              C.sub.6 H.sub.4 Cl                                                                   II.80                         COOC.sub.2 H.sub.5                                                                  NHCOC(CH.sub.3).sub.3                                                                        COC.sub.6 H.sub.4 N(CH.sub.3).sub.2                                                               C.sub.6 H.sub.4 N(CH.sub.3).sub.2                                             2      II.81                         CN    NH.sub.2                                                                                      ##STR188##                II.82                         CN    OC.sub.6 H.sub.4 C.sub.16 H.sub.33                                                           C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                          H      II.83                         CN                                                                                   ##STR189##                                                                                   ##STR190##         H      II.84                         CN                                                                                   ##STR191##                                                                                   ##STR192##         H      II.85                         CN    NHCOOC.sub.2 H.sub.5                                                                          ##STR193##         H      II.86                         CN    NHCOOC.sub.2 H.sub.5                                                                          ##STR194##         H      II.87                         CN    NHCOCHCH.sub.2                                                                                ##STR195##         H      II.88                         CN                                                                                   ##STR196##                                                                                   ##STR197##         H      II.89                         CN    N(CH.sub.2 C.sub.6 H.sub.5).sub.2                                                             ##STR198##         H      II.90                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                  C.sub.6 H.sub.4 N(CH.sub.2 COOCH.sub.3).sub.2                                                     H      II.91                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR199##         H      II.92                         CN    N(CH.sub.2 C.sub.6 H.sub.5).sub.2                                                             ##STR200##                II.93                         CN    N(C.sub.3 H.sub.7).sub.2                                                                      ##STR201##         H      II.94                         CN    NHCOC.sub.15 H.sub.31                                                                         ##STR202##         H      II.95                         CN                                                                                   ##STR203##                                                                                   ##STR204##         H      II.96                         CN    N(COO(C.sub.2 H.sub.4 O).sub.3 CO).sub.2                                                      ##STR205##         H      II.97                         CN                                                                                   ##STR206##                                                                                   ##STR207##         H      II.98                         CN    NHCOOC.sub.2 H.sub.5                                                                          ##STR208##         H      II.99                         CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR209##         H      II.100                        CN    N(CH.sub.2 C.sub.6 H.sub.5).sub.2                                                             ##STR210##         H      II.101                        COOCH.sub.3                                                                          ##STR211##                                                                                   ##STR212##         H      II.102                        CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR213##         H      II.103                        COOC.sub.2 H.sub.5                                                                   ##STR214##                                                                                   ##STR215##                II.104                        CN    NHCOOC(CH.sub.3).sub.3                                                                        ##STR216##                II.105                        CN                                                                                   ##STR217##                                                                                   ##STR218##                II.106                        CN                                                                                   ##STR219##                                                                                   ##STR220##                II.107                        CN    NH.sub.2                                                                                      ##STR221##                II.108                        CN                                                                                   ##STR222##                                                                                   ##STR223##                II.109                        CN    NH.sub.2                                                                                      ##STR224##         H      II.110                        CN    NH.sub.2                                                                                      ##STR225##         H      II.111                        CN    NH.sub.2                                                                                      ##STR226##         H      II.112                        CN    NH.sub.2                                                                                      ##STR227##         H      II.113                        CN                                                                                   ##STR228##                                                                                   ##STR229##                II.114                        CN    N(COOC.sub.4 H.sub.9).sub.2                                                                   ##STR230##                II.115                        CN    N(COOCH.sub.2 CH(CH.sub.3).sub.2).sub.2                                                       ##STR231##                II.116                        CN    NHCOOCH.sub.2 CH(CH.sub.3).sub.2                                                              ##STR232##                II.117                        CN    N(COOCH.sub.2 CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9).sub.2                                       ##STR233##                II.118                        CN                                                                                   ##STR234##                                                                                   ##STR235##                II.119                        CN                                                                                   ##STR236##                                                                                   ##STR237##                II.120                        CN                                                                                   ##STR238##                                                                                   ##STR239##                II.121                        CN                                                                                   ##STR240##                                                                                   ##STR241##                II.122                        CN                                                                                   ##STR242##                                                                                   ##STR243##                II.123                        CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR244##                II.124                        CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR245##                II.125                        CN    NH.sub.2                                                                                      ##STR246##                II.126                        CN    NH.sub.2                                                                                      ##STR247##         H      II.127                        CN    NH.sub.2                                                                                      ##STR248##         H      II.128                        CN    NH.sub.2                                                                                      ##STR249##         H      II.129                        CN    NH.sub.2                                                                                      ##STR250##         H      II.130                        CN    N(COOC.sub.2 H.sub.5).sub.2                                                                   ##STR251##         H      II.131                        CN                                                                                   ##STR252##    C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                          H      II.132                        CN                                                                                   ##STR253##    C.sub.6 H.sub.4 N(C.sub.2 H.sub.5).sub.2                                                          H      II.133                        __________________________________________________________________________

Dyes according to formula (II) can be obtained by addition of amalononitrile dimer to an electrophilic center R⁹ --CO--R¹⁰ such asaldehydes, ketones, enonen, esters, etc. This addition can be carriedout using a base as catalyst.

The synthesis of dyes according to formula (II) wherein Y representsNH₂, is described by H. Junek, B. Hornischer and H. Hambock inMonatshefte fur Chemie, Vol. 100, 1969, pages 503 to 509.

Dyes according to formula (II) wherein Y is not NH₂ or wherein R⁹ andR¹⁰ together with the C atom to which they are attached represent thenecessary atoms to close a pyrone-type nucleus have not been describedbefore. The synthesis of pyrones is described in Organic Synthesis, Vol.46, 1966, pages 57 to 62.

Among the dyes according to formula (II) those wherein Z is CN and Y isNR⁵ R⁶ are preferred; and among those the dyes wherein R⁹ and R¹⁰together with the C atom to which they are attached represent thenecessary atoms to close a pyrone-type nucleus are preferred.

The dyes according to the present invention wherein X represents N-NR¹¹R¹², can be represented by the following formula (III) ##STR254##wherein Z, Y, R¹¹ and R¹² are defined as hereinbefore.

Representative examples of dyes according to formula (III) are listedbelow in table 3.

                                      TABLE 3                                     __________________________________________________________________________    Z  Y          R.sup.11           R.sup.12                                                                            no.                                    __________________________________________________________________________    CN NH.sub.2                                                                                  ##STR255##        H     III.1                                  CN NH.sub.2                                                                                  ##STR256##        H     III.2                                  CN NH.sub.2                                                                                  ##STR257##        H     III.3                                  CN NH.sub.2                                                                                  ##STR258##        H     III.4                                  CN NH.sub.2                                                                                  ##STR259##        H     III.5                                  CN NH.sub.2                                                                                  ##STR260##        H     III.6                                  CN NH.sub.2                                                                                  ##STR261##        H     III.7                                  CN NH.sub.2                                                                                  ##STR262##        H     III.8                                  CN NH.sub.2                                                                                  ##STR263##        H     III.9                                  CN N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR264##        COOC.sub.2 H.sub.5                                                                  III.10                                 CN NHCOOC.sub.2 H.sub.5                                                                      ##STR265##        COOC.sub.2 H.sub.5                                                                  III.11                                 CN NHCH(CH.sub.3).sub.2                                                                      ##STR266##        SO.sub.2 C.sub.6 H.sub.5                                                            III.12                                 CN NHCOCH.sub.3                                                                              ##STR267##        H     III.13                                 CN NCOOC.sub.4 H.sub.9                                                                       ##STR268##        COOC.sub.4 H.sub.9                                                                  III.14                                 CN                                                                                ##STR269##                                                                               ##STR270##        CH.sub.3                                                                            III.15                                 CN                                                                                ##STR271##                                                                               ##STR272##        CH.sub.3                                                                            III.16                                 CN NHCOC.sub.2 H.sub.5                                                                       ##STR273##        COC.sub.2 H.sub.5                                                                   III.17                                 CN                                                                                ##STR274##                                                                               ##STR275##        H     III.18                                 CN N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR276##        COOC.sub.2 H.sub.5                                                                  III.19                                 CN N(COOCH.sub.3).sub.2                                                                      ##STR277##        COOCH.sub.3                                                                         III.20                                 CN                                                                                ##STR278##                                                                               ##STR279##        H     III.21                                 CN N(COOC.sub.4 H.sub.9).sub.2                                                               ##STR280##        COOC.sub.4 H.sub.9                                                                  III.22                                 CN NHCOCH.sub.3                                                                              ##STR281##        COCH.sub.3                                                                          III.23                                 CN N(CH.sub.3).sub.2                                                                         ##STR282##        CH.sub.3                                                                            III.24                                 CN                                                                                ##STR283##                                                                               ##STR284##        H     III.25                                 __________________________________________________________________________

Dyes according to formula (III) can be obtained by addition of amalononitrile dimer to a diazonium compound. This addition can becarried out using a base as catalyst.

The synthesis of these dyes is described in DE 2922227 and inZeitschrift fur Chemie, Vol. 29, 1989, pages 66 to 67 for reactions withmalononitrile.

The dyes according to the present invention wherein X representsN--N═CR¹³ R¹⁴, can be represented by the following formula (IV)##STR285## wherein Z, Y, R¹³ and R¹⁴ are defined as hereinbefore.

In a particular type of dye according to formula (IV), R¹³ and R¹⁴together with the C atom to which they are attached represent thenecessary atoms to close a heterocyclic nucleus represented by##STR286## wherein n represents 0, 1 or 2;

P and Q (same or different) represent a methine group or a substitutedmethine group;

R²⁸ represents substituted or unsubstituted alkyl, substituted orunsubstituted cycloalkyl, substituted or unsubstituted aryl and

A represents a bond or the necessary atoms to close anitrogen-containing heterocyclic nucleus including said nucleus insubstituted form.

Representative examples of dyes according to formula (IV) are listedbelow in table 4.

                                      TABLE 4                                     __________________________________________________________________________    Z     Y          R.sup.13         R.sup.14                                                                         no.                                      __________________________________________________________________________    CN    NH.sub.2                                                                                  ##STR287##         IV.1                                     CN                                                                                   ##STR288##                                                                               ##STR289##         IV.2                                     CN                                                                                   ##STR290##                                                                               ##STR291##         IV.3                                     CN                                                                                   ##STR292##                                                                               ##STR293##         IV.4                                     CN                                                                                   ##STR294##                                                                               ##STR295##         IV.5                                     CN                                                                                   ##STR296##                                                                               ##STR297##         IV.6                                     CN    N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR298##         IV.7                                     CN                                                                                   ##STR299##                                                                               ##STR300##         IV.8                                     CN                                                                                   ##STR301##                                                                               ##STR302##         IV.9                                     COOC.sub.2 H.sub.5                                                                   ##STR303##                                                                               ##STR304##         IV.10                                    COOC.sub.2 H.sub.5                                                                   ##STR305##                                                                               ##STR306##         IV.11                                    CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                      ##STR307##         IV.12                                    CN                                                                                   ##STR308##                                                                               ##STR309##         IV.13                                    CN    OCH.sub.2 C.sub.6 H.sub.5                                                                 ##STR310##         IV.14                                    CN    NH.sub.2                                                                                  ##STR311##         IV.15                                    CN                                                                                   ##STR312##                                                                               ##STR313##         IV.16                                    CN                                                                                   ##STR314##                                                                               ##STR315##         IV.17                                    CN                                                                                   ##STR316##                                                                               ##STR317##         IV.18                                    CN                                                                                   ##STR318##                                                                               ##STR319##         IV.19                                    CN                                                                                   ##STR320##                                                                               ##STR321##         IV.20                                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR322##         IV.21                                    CN                                                                                   ##STR323##                                                                               ##STR324##         IV.22                                    CN                                                                                   ##STR325##                                                                               ##STR326##         IV.23                                    COOC.sub.2 H.sub.5                                                                   ##STR327##                                                                               ##STR328##         IV.24                                    COOC.sub.2 H.sub.5                                                                   ##STR329##                                                                               ##STR330##         IV.25                                    CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                      ##STR331##         IV.26                                    CN                                                                                   ##STR332##                                                                               ##STR333##         IV.27                                    CN    OCH.sub.2 C.sub.6 H.sub.5                                                                 ##STR334##         IV.28                                    CN    NH.sub.2                                                                                  ##STR335##         IV.29                                    CN                                                                                   ##STR336##                                                                               ##STR337##         IV.30                                    CN                                                                                   ##STR338##                                                                               ##STR339##         IV.31                                    CN                                                                                   ##STR340##                                                                               ##STR341##         IV.32                                    CN                                                                                   ##STR342##                                                                               ##STR343##         IV.33                                    CN                                                                                   ##STR344##                                                                               ##STR345##         IV.34                                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR346##         IV.35                                    CN                                                                                   ##STR347##                                                                               ##STR348##         IV.36                                    CN                                                                                   ##STR349##                                                                               ##STR350##         IV.37                                    COOC.sub.2 H.sub.5                                                                   ##STR351##                                                                               ##STR352##         IV.38                                    COOC.sub.2 H.sub.5                                                                   ##STR353##                                                                               ##STR354##         IV.39                                    CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                      ##STR355##         IV.40                                    CN                                                                                   ##STR356##                                                                               ##STR357##         IV.41                                    CN    OCH.sub.2 C.sub.6 H.sub.5                                                                 ##STR358##         IV.42                                    CN    NH.sub.2                                                                                  ##STR359##         IV.43                                    CN                                                                                   ##STR360##                                                                               ##STR361##         IV.44                                    CN                                                                                   ##STR362##                                                                               ##STR363##         IV.45                                    CN                                                                                   ##STR364##                                                                               ##STR365##         IV.46                                    CN                                                                                   ##STR366##                                                                               ##STR367##         IV.47                                    CN                                                                                   ##STR368##                                                                               ##STR369##         IV.48                                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR370##         IV.49                                    CN                                                                                   ##STR371##                                                                               ##STR372##         IV.50                                    CN                                                                                   ##STR373##                                                                               ##STR374##         IV.51                                    COOC.sub.2 H.sub.5                                                                   ##STR375##                                                                               ##STR376##         IV.52                                    COOC.sub.2 H.sub.5                                                                   ##STR377##                                                                               ##STR378##         IV.53                                    CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                      ##STR379##         IV.54                                    CN                                                                                   ##STR380##                                                                               ##STR381##         IV.55                                    CN    OCH.sub.2 C.sub.6 H.sub.5                                                                 ##STR382##         IV.56                                    CN    NH.sub.2                                                                                  ##STR383##         IV.57                                    CN                                                                                   ##STR384##                                                                               ##STR385##         IV.58                                    CN                                                                                   ##STR386##                                                                               ##STR387##         IV.59                                    CN                                                                                   ##STR388##                                                                               ##STR389##         IV.60                                    CN                                                                                   ##STR390##                                                                               ##STR391##         IV.61                                    CN                                                                                   ##STR392##                                                                               ##STR393##         IV.62                                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR394##         IV.63                                    CN                                                                                   ##STR395##                                                                               ##STR396##         IV.64                                    CN                                                                                   ##STR397##                                                                               ##STR398##         IV.65                                    COOC.sub.2 H.sub.5                                                                   ##STR399##                                                                               ##STR400##         IV.66                                    COOC.sub.2 H.sub.5                                                                   ##STR401##                                                                               ##STR402##         IV.67                                    CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                      ##STR403##         IV.68                                    CN                                                                                   ##STR404##                                                                               ##STR405##         IV.69                                    CN    OCH.sub.2 C.sub.6 H.sub.5                                                                 ##STR406##         IV.70                                    CN    NH.sub.2                                                                                  ##STR407##         IV.71                                    CN                                                                                   ##STR408##                                                                               ##STR409##         IV.72                                    CN                                                                                   ##STR410##                                                                               ##STR411##         IV.73                                    CN                                                                                   ##STR412##                                                                               ##STR413##         IV.74                                    CN                                                                                   ##STR414##                                                                               ##STR415##         IV.75                                    CN                                                                                   ##STR416##                                                                               ##STR417##         IV.76                                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR418##         IV.77                                    CN                                                                                   ##STR419##                                                                               ##STR420##         IV.78                                    CN                                                                                   ##STR421##                                                                               ##STR422##         IV.79                                    COOC.sub.2 H.sub.5                                                                   ##STR423##                                                                               ##STR424##         IV.80                                    COOC.sub.2 H.sub.5                                                                   ##STR425##                                                                               ##STR426##         IV.81                                    CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                      ##STR427##         IV.82                                    CN                                                                                   ##STR428##                                                                               ##STR429##         IV.83                                    CN    OCH.sub.2 C.sub.6 H.sub.5                                                                 ##STR430##         IV.84                                    CN    NH.sub.2                                                                                  ##STR431##         IV.85                                    CN                                                                                   ##STR432##                                                                               ##STR433##         IV.86                                    CN                                                                                   ##STR434##                                                                               ##STR435##         IV.87                                    CN                                                                                   ##STR436##                                                                               ##STR437##         IV.88                                    CN                                                                                   ##STR438##                                                                               ##STR439##         IV.89                                    CN                                                                                   ##STR440##                                                                               ##STR441##         IV.90                                    CN    N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR442##         IV.91                                    CN                                                                                   ##STR443##                                                                               ##STR444##         IV.92                                    CN                                                                                   ##STR445##                                                                               ##STR446##         IV.93                                    COOC.sub.2 H.sub.5                                                                   ##STR447##                                                                               ##STR448##         IV.94                                    COOC.sub.2 H.sub.5                                                                   ##STR449##                                                                               ##STR450##         IV.95                                    CN    N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                      ##STR451##         IV.96                                    CN                                                                                   ##STR452##                                                                               ##STR453##         IV.97                                    CN    OCH.sub.2 C.sub.6 H.sub.5                                                                 ##STR454##         IV.98                                    CN    NH.sub.2                                                                                  ##STR455##         IV.99                                    CN                                                                                   ##STR456##                                                                               ##STR457##          IV.100                                  CN                                                                                   ##STR458##                                                                               ##STR459##          IV.101                                  CN                                                                                   ##STR460##                                                                               ##STR461##          IV.102                                  CN                                                                                   ##STR462##                                                                               ##STR463##          IV.103                                  CN                                                                                   ##STR464##                                                                               ##STR465##          IV.104                                  CN    N(COOC.sub.2 H.sub.5).sub.2                                                               ##STR466##          IV.105                                  CN                                                                                   ##STR467##                                                                               ##STR468##          IV.106                                  CN                                                                                   ##STR469##                                                                               ##STR470##          IV.107                                  COOC.sub.2 H.sub.5                                                                   ##STR471##                                                                               ##STR472##          IV.108                                  CN                                                                                   ##STR473##                                                                               ##STR474##          IV.109                                  CN    OCH.sub.2 C.sub.6 H.sub.5                                                                 ##STR475##          IV.110                                  CN    NH.sub.2                                                                                  ##STR476##          IV.111                                  __________________________________________________________________________

Dyes according to formula (IV) can be obtained by addition of amalononitrile dimer to a hydrazone compound in the presence of anoxidizing agent. The synthesis of hydrazone compounds is described inFR-P 1444971 and in GB-P 1301657.

Dyes according to formula (IV) have not been described before.

According to another embodiment of this invention wherein X representsN-Het with Het being a heterocyclic nucleus, the dyes correspond togeneral formula (V) ##STR477## wherein Z and Y are as definedhereinbefore;

R²⁹ represents hydrogen or any substituent e.g. substituted orunsubstituted alkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted aryl, carboxyl esters, carboxyl amides,amino, acylamino;

R³⁰ represents hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted cycloalkyl, substituted or unsubstituted aryl or aheterocyclic residue and

R³¹ represents hydrogen, substituted or unsubstituted alkyl, substitutedor unsubstituted cycloalkyl, substituted or unsubstituted aryl, acyl ora heterocyclic residue.

Representative examples of dyes according to formula (V) are listedbelow in table 5.

                  TABLE 5                                                         ______________________________________                                        Z       Y               R.sup.29                                                                              R.sup.30                                                                           R.sup.31                                                                           no.                                 ______________________________________                                        CN      NH.sub.2        CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.1                                 CN                                                                                     ##STR478##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.2                                 CN                                                                                     ##STR479##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.3                                 CN                                                                                     ##STR480##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.4                                 CN                                                                                     ##STR481##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.5                                 CN                                                                                     ##STR482##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.6                                 CN      N(COOC.sub.2 H.sub.5).sub.2                                                                   CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.7                                 CN                                                                                     ##STR483##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.8                                 CN                                                                                     ##STR484##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.9                                 COOC.sub.2 H.sub.5                                                                     ##STR485##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.10                                COOC.sub.2 H.sub.5                                                                     ##STR486##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.11                                CN      N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                          CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.12                                CN                                                                                     ##STR487##     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.13                                CN      OCH.sub.2 C.sub.6 H.sub.5                                                                     CH.sub.3                                                                              CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.14                                CN      NH.sub.2        C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.15                                CN                                                                                     ##STR488##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.16                                CN                                                                                     ##STR489##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.17                                CN                                                                                     ##STR490##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.18                                CN                                                                                     ##STR491##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.19                                CN                                                                                     ##STR492##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.20                                CN      N(COOC.sub.2 H.sub.5).sub.2                                                                   C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.21                                CN                                                                                     ##STR493##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.22                                CN                                                                                     ##STR494##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.23                                COOC.sub.2 H.sub.5                                                                     ##STR495##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.24                                COOC.sub.2 H.sub.5                                                                     ##STR496##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.25                                CN      N(COOCH.sub.2 C.sub.6 H.sub.5).sub.2                                                          C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.26                                CN                                                                                     ##STR497##     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.27                                CN      OCH.sub.2 C.sub.6 H.sub.5                                                                     C.sub.13 H.sub.25                                                                     CH.sub.3                                                                           CH.sub.3                                                                           V.28                                CN      NH.sub.2        C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.29                                CN                                                                                     ##STR498##     C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.30                                CN      N(COOC.sub.2 H.sub.5).sub.2                                                                   C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.31                                CN                                                                                     ##STR499##     C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    V.32                                CN      NH.sub.2        CH.sub.3                                                                              C.sub.3 H.sub.7                                                                    C.sub.6 H.sub.5                                                                    V.33                                CN                                                                                     ##STR500##     CH.sub.3                                                                              C.sub.3 H.sub.7                                                                    C.sub.6 H.sub.5                                                                    V.34                                CN      N(COOC.sub.4 H.sub.9).sub.2                                                                   CH.sub.3                                                                              C.sub.3 H.sub.7                                                                    C.sub.6 H.sub.5                                                                    V.35                                ______________________________________                                    

Dyes according to formula (V) can be obtained by addition of amalononitrile dimer to an antipyrine nucleus in the presence of anoxidizing agent. Derivatization of the --NH₂ group is done by methods asdescribed below in the examples. These dyes have not been describedbefore.

The present dyes are of cyan, magenta or yellow hue.

These dyes can be used in inks e.g. for laser applications and ininkjet, in textile, in lacquers and in paints.

These dyes are particularly useful in thermal dye sublimation ordiffusion transfer applications including laser-induced transfer andresistive ribbon transfer. However, they can also be used in thermal dyemelt transfer.

According to a particular embodiment of this invention the present dyesare used in the dye layer of a dye-donor element for thermal dyesublimation transfer.

For improving the stability of the dyes to light, the use of a metalcomplex of the dye, e.g. a Ni or Co complex, is also effective.

The dye layer is formed preferably by adding the dyes, the polymericbinder medium, and other optional components to a suitable solvent orsolvent mixture, dissolving or dispersing the ingredients to form acoating composition that is applied to a support, which may have beenprovided first with an adhesive or subbing layer, and dried.

The dye layer thus formed has a thickness of about 0.2 to 5.0 μm,preferably 0.4 to 2.0 μm, and the amount ratio of dye to binder isbetween 9:1 and 1:3 by weight, preferably between 2:1 and 1:2 by weight.

As polymeric binder the following can be used: cellulose derivatives,such as ethyl cellulose, hydroxyethyl cellulose, ethylhydroxy cellulose,ethylhydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose,nitrocellulose, cellulose acetate formate, cellulose acetate hydrogenphthalate, cellulose acetate, cellulose acetate propionate, celluloseacetate butyrate, cellulose acetate pentanoate, cellulose acetatebenzoate, cellulose triacetate; vinyl-type resins and derivatives, suchas polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, copolyvinylbutyral-vinyl acetal-vinyl alcohol, polyvinyl pyrrolidone, polyvinylacetoacetal, polyacrylamide; polymers and copolymers derived fromacrylates and acrylate derivatives, such as polyacrylic acid, polymethylmethacrylate and styrene-acrylate copolymers; polyester resins;polycarbonates; copolystyrene-acrylonitrile; polysulfones; polyphenyleneoxide; organosilicones, such as polysiloxanes; epoxy resins and naturalresins, such as gum arabic.

Particularly preferred dyes or dye mixtures for use in a dye-donorelement for thermal dye sublimation are: for yellow a mixture of dyeII.116 and a dye corresponding to the formula ##STR501## in a ratio of1:10 to 10:1, for magenta a mixture of a dye corresponding to theformula ##STR502## and a dye corresponding to the formula ##STR503## ina ratio of 1:10 to 10:1, or a mixture of a dye corresponding to theformula ##STR504## and a dye corresponding to the formula ##STR505## ina ratio of 1:10 to 10:1, and for cyan a mixture of dye I.134 and dyeI.92 or dye I.96 in a ratio of 1:10 to 10:1. The binder that ispreferably used in the dye layer is a mixture ofco-styrene-acrylonitrile and co-styrene-acrylonitrile-butadiene in aratio ranging from 0 to 100% of either of the constituents. Preferablythe binder/dye ratio is between 5:1 and 1:5.

The coating layer may also contain other additives, such as curingagents, preservatives, etc., these and other ingredients being describedmore fully in EP 133011, EP 133012, EP 111004 and EP 279467.

Any material can be used as the support for the dye-donor elementprovided it is dimensionally stable and capable of withstanding thetemperatures involved, up to 400° C. over a period of up to 20 msec, andis yet thin enough to transmit heat applied on one side through to thedye on the other side to effect transfer to the receiver sheet withinsuch short periods, typically from 1 to 10 msec. Such materials includepolyesters such as polyethylene terephthalate, polyamides,polyacrylates, polycarbonates, cellulose esters, fluorinated polymers,polyethers, polyacetals, polyolefins, polyimides, glassine paper andcondenser paper. Preference is given to a support comprisingpolyethylene terephthalate. In general, the support has a thickness of 2to 30 μm. The support may also be coated with an adhesive or subbinglayer, if desired.

The dye layer of the dye-donor element may be coated on the support orprinted thereon by a printing technique such as a gravure process.

A dye-barrier layer comprising a hydrophilic polymer may also beemployed in the dye-donor element between its support and the dye layerto improve the dye transfer densities by preventing wrong-way transferof dye towards the support. The dye barrier layer may contain anyhydrophilic material which is useful for the intended purpose. Ingeneral, good results have been obtained with gelatin, polyacryl amide,polyisopropyl acrylamide, butyl methacrylate grafted gelatin, ethylmethacrylate grafted gelatin, ethyl acrylate grafted gelatin, cellulosemonoacetate, methyl cellulose, polyvinyl alcohol, polyethylene imine,polyacrylic acid, a mixture of polyvinyl alcohol and polyvinyl acetate,a mixture of polyvinyl alcohol and polyacrylic acid or a mixture ofcellulose monoacetate and polyacrylic acid. Suitable dye barrier layershave been described in e.g. EP 227091 and EP 228065. Certain hydrophilicpolymers, for example those described in EP 227091, also have anadequate adhesion to the support and the dye layer, thus eliminating theneed for a separate adhesive or subbing layer. These particularhydrophilic polymers used in a single layer in the donor element thusperform a dual function, hence are referred to as dye-barrier/subbinglayers.

Preferably the reverse side of the dye-donor element can be coated witha slipping layer to prevent the printing head from sticking to thedye-donor element. Such a slipping layer would comprise a lubricatingmaterial such as a surface active agent, a liquid lubricant, a solidlubricant or mixtures thereof, with or without a polymeric binder. Thesurface active agents may be any agents known in the art such ascarboxylates, sulfonates, phosphates, aliphatic amine salts, aliphaticquaternary ammonium salts, polyoxyethylene alkyl ethers, polyethyleneglycol fatty acid esters, fluoroalkyl C₂ -C₂₀ aliphatic acids. Examplesof liquid lubricants include silicone oils, synthetic oils, saturatedhydrocarbons and glycols. Examples of solid lubricants include varioushigher alcohols such as stearyl alcohol, fatty acids and fatty acidesters. Suitable slipping layers are described in e.g. EP 138483, EP227090, U.S. Pat. Nos. 4,567,113, 4,572,860, 4,717,711. Preferably theslipping layer comprises as binder a styrene-acrylonitrile copolymer ora styrene-acrylonitrile-butadiene copolymer or a mixture hereof and aslubricant in an amount of 0.1 to 10% by weight of the binder (mixture) apolysiloxane-polyether copolymer or polytetrafluoroethylene or a mixturehereof.

The support for the receiver sheet that is used with the dye-donorelement may be a transparant film of e.g. polyethylene terephthalate, apolyether sulfone, a polyimide, a cellulose ester or a polyvinylalcohol-co-acetal. The support may also be a reflective one such asbaryta-coated paper, polyethylene-coated paper or white polyester i.e.white-pigmented polyester.

To avoid poor adsorption of the transferred dye to the support of thereceiver sheet this support must be coated with a special surface, adye-image-receiving layer, into which the dye can diffuse more readily.The dye-image-receiving layer may comprise, for example, apolycarbonate, a polyurethane, a polyester, a polyamide, polyvinylchloride, polystyrene-co-acrylonitrile, polycaprolactone or mixturesthereof. Suitable dye-receiving layers have been described in e.g. EP133011, EP 133012, EP 144247, EP 227094, EP 228066.

In order to improve the light resistance and other stabilities ofrecorded images, UV absorbers, singlet oxygen quenchers such asHALS-compounds (Hindered Amine Light Stabilizers) and/or antioxidantsmay be incorporated into the receiving layer.

The dye layer of the dye-donor element or the dye-image-receiving layerof the receiver sheet may also contain a releasing agent that aids inseparating the dye-donor element from the dye-receiving element aftertransfer. The releasing agents can also be applied in a separate layeron at least part of the dye layer or of the receiving layer. For thereleasing agent solid waxes, fluorine- or phosphate-containingsurfactants and silicone oils are used. Suitable releasing agents aredescribed in e.g. EP 133012, JP 85/19138, EP 227092.

The dye-donor elements according to the invention are used to form a dyetransfer image. Such a process comprises placing the dye layer of thedonor element in face-to-face relation with the dye-receiving layer ofthe receiver sheet and imagewise heating from the back of the donorelement. The transfer of the dye is accomplished by heating for aboutseveral milliseconds at a temperature of 400° C.

When the process is performed for but one single color, a monochrome dyetransfer image is obtained. A multicolor image can be obtained by usinga donor element containing three or more primary color dyes andsequentially performing the process steps described above for eachcolor. The above sandwich of donor element and receiver sheet is formedon three occasions during the time when heat is applied by the thermalprinting head. After the first dye has been transferred, the elementsare peeled apart. A second dye-donor element (or another area of thedonor element with a different dye area) is then brought in registerwith the dye-receiving element and the process repeated. The third colorand optionally further colors are obtained in the same manner.

In order to accomplish a perfect register when the process is performedfor more than one color and in order to detect what color is existing atthe printing portion of the donor element, detection marks are commonlyprovided on one surface of the donor element. Generally opticallydetectable marks are used that can be detected by a light source and aphoto sensor; detection being done by measuring the light transmittedthrough the detection mark or reflected from said mark. The marks beingin the form of a light-absorbing or light-reflecting coating are formedin a preassigned position on the donor element by e.g. gravure printing.The detection marks can comprise an infrared shielding compound such ascarbon black. The detection mark can also comprise one of the image dyesthat are used for the image formation, with the detection being in thevisible range.

The receiving element can also have detection marks provided on onesurface, preferably the back surface so that the receiving element canbe accurately set at a desired position during transfer, whereby theimage can be formed always at a correct desired position.

In addition to thermal heads, laser light, infrared flash or heated penscan be used as the heat source for supplying heat energy. Thermalprinting heads that can be used to transfer dye from the dye-donorelements of the present invention to a receiver sheet are commerciallyavailable. In case laser light is used, the dye layer or another layerof the dye element has to contain a compound that absorbs the lightemitted by the laser and converts it into heat, e.g. carbon black.

Alternatively, the support of the dye-donor element may be anelectrically resistive ribbon consisting of, for example, a multi-layerstructure of a carbon loaded polycarbonate coated with a thin aluminumfilm. Current is injected into the resistive ribbon by electricallyadressing a print head electrode resulting in highly localized heatingof the ribbon beneath the relevant electrode. The fact that in this casethe heat is generated directly in the resistive ribbon and that it isthus the ribbon that gets hot leads to an inherent advantage in printingspeed using the resistive ribbon/electrode head technology compared tothe thermal head technology where the various elements of the thermalhead get hot and must cool down before the head can move to the nextprinting position.

The following examples are provided to illustrate the invention in moredetail without limiting, however, the scope thereof.

EXAMPLE 1 Synthesis of Dye I.1

2.92 g of dye I.61, 60 ml of acetone, 6.9 g of potassium carbonate and4.76 ml of benzylbromide were added together and the mixture wasrefluxed for 1 hours. The potassium carbonate was filtered and washedwith dichloromethane. The filtrate was concentrated by evaporation andwas dried under vacuum. 3 g of dye I.1 was obtained.

EXAMPLE 2 Synthesis of Dye I.6

6.98 g of dye I.13, 50 ml of dichloromethane, 150 ml of toluene, 22.3 mlof triethylamine and 8 g of succinic anhydride were added together andwere stirred for 4 hours at room temperature. The mixture was leftovernight. The residue was filtered and the filtrate was diluted with750 ml of ethylacetate. The mixture was extracted four times with 1 l ofwater and two times with 500 ml of saturated sodium chloride and driedover sodium sulfate. After filtration the solution was concentrated byevaporation. 3 g of dye I.6 was obtained. Dye I.6 was purified by columnchromatography using as eluent dichloromethane/ethylacetate 96:4.

EXAMPLE 3 Synthesis of Dye I.13

31.2 g of 3-acetamido-4-nitroso-diethylaniline and 19 g of malononitriledimer and 360 ml of ethanol were added together and heated whilestirring. Triethylamine (16.7 ml) was added. The mixture was stirred for24 hours at 25° C. The precipitate was filtered, washed with ethanol,methanol and hexane. 33 g of dye I.13 was obtained.

EXAMPLE 4 Synthesis of Dye I.22

6.98 g of dye I.13, 50 ml of dichloromethane, 150 ml of toluene, 22.3 mlof triethylamine and 11.9 g of phthalic anhydride were added togetherand were stirred for 10 minutes at room temperature. The reactionmixture was diluted with 1 l of ethylacetate. The mixture was extractedwith 1 l of 1N hydrogen chloride, five times with 1 l of water and twotimes with 500 ml of saturated sodium chloride and dried over sodiumsulfate. After filtration the solution was concentrated by evaporation.After purification by column chromatography (eluent dichloromethane) 7.4g of dye I.22 was obtained.

EXAMPLE 5 Synthesis of Dye I.28

2.5 g of dye I.13, 40 ml of dichloromethane and 2.9 ml of pyridine wereadded together at 10°-20° C. while stirring. 3.43 ml ofethylchloroformate was added dropwise and the mixture was stirred for 2hours at room temperature. An extra amount of 0.29 ml of pyridine and0.343 ml of ethylchloroformate was added. The mixture was stirred for 2hours at room temperature. 300 ml of ethylacetate was added. The mixturewas extracted with 250 ml of 1N hydrogen chloride, five times with 400ml of water and two times with 250 ml of saturated sodium chloride anddried over sodium sulfate. After filtration the solution wasconcentrated by evaporation and dried under vacuum. Afterrecrystallization (solvent mixture: 20 ml of methylethylketone and 60 mlof ethanol) 2.33 g of dye I.28 was obtained.

EXAMPLE 6 Synthesis of Dye I.30

4 g of dye I.61, 60 ml of dichloromethane and 5.74 ml of triethylaminewere added together and 3.2 ml of methanesulfonyl chloride was addeddropwise hereto at 0°-10° C. After 15 minutes of stirring at roomtemperature an extra amount of 5.74 ml of triethylamine was added. After1 hour of stirring at room temperature the reaction mixture was dilutedwith 300 ml of ethylacetate. The mixture was extracted four times with300 ml of water and two times with 300 ml of saturated sodium chlorideand dried over sodium sulfate. After filtration the solution wasconcentrated by evaporation and dried under vacuum. 4.5 g of dye I.30was obtained.

EXAMPLE 7 Synthesis of Dye I.37

2 g of dye I.97 was dissolved in 30 ml of dichloromethane and 3 mlpyridine were added. Subsequently 3.4 ml of ethyl chloroformate wasadded dropwise hereto while stirring at 5°-10° C. After 24 hours ofstirring at room temperature 200 ml of dichloromethane was added to thereaction mixture and extracted with 500 ml of 0.1N hydrogen chloride andwashed with water till neutral and dried on magnesium sulfate. Afterfiltration the solution was concentrated by evaporation, recrystallizedusing 40 ml of ethanol and dried under vacuum. 1.3 g of dye I.37 wasobtained.

EXAMPLE 8 Synthesis of Dye I.61

20 g of 4-nitroso-N-diethylaniline and 18.92 g of malononitrile dimerand 240 ml of ethanol were added together and were heated whilestirring. 20 drops of piperidine were added. The mixture was refluxedfor 2 hours while stirring and was then left overnight at roomtemperature without stirring. The crystals were filtered and washedthree times with 100 ml of ethanol and three times with 100 ml ofn-hexane and dried under vacuum. 28.5 g of dye I.61 were obtained.

EXAMPLE 9 Synthesis of Dye I.77

21.5 g of 3-methyl-4-nitroso-N-diethylaniline and 15.52 g ofmalononitrile dimer and 240 ml of ethanol were added together and wereheated while stirring. 26 drops of piperidine were added. An extraamount of 100 ml of ethanol were added to facilitate the stirring. Themixture was refluxed for 2 hours and was then left overnight at roomtemperature without stirring. The crystals were filtered and washed fivetimes with 50 ml of ethanol and three times with 100 ml of n-hexane anddried under vacuum. 30 g of dye I.32 were obtained.

2.1 g of dye I.32, 30 ml of dichloromethane and 6 ml of pyridine wereadded together at 0° C. While stirring 6 ml of ethylchloroformate wereadded dropwise. The mixture was stirred for 36 hours at roomtemperature. The reaction mixture was diluted with 300 ml ofethylacetate. The mixture was extracted with 250 ml of 1N hydrogenchloride, five times with 250 ml of water and two times with 250 ml ofsaturated sodium chloride and dried over magnesium sulfate. Afterfiltration the solution was concentrated by evaporation and dried undervacuum. After recrystallization with ethanol (60 ml) 2.25 g of dye I.77was obtained.

EXAMPLE 10 Synthesis of Dye I.91

6 g of dye I.61, 100 ml of dichloromethane, 200 ml of toluene, 22.2 mlof triethylamine and 24.32 g of tetrachlorophthalic anhydride were addedtogether and the mixture was stirred for 2.5 hours at room temperature.The reaction mixture was diluted with 1 l of ethylacetate. The mixturewas extracted five times with 500 ml of water and two times with 250 mlof saturated sodium chloride and dried over magnesium sulfate. Afterfiltration the solution was concentrated by evaporation and dried undervacuum to obtain pure dye I.91.

EXAMPLE 11 Synthesis of Dye I.97

5 g of the below identified compound and 2.8 g of malononitrile dimerwere added in 100 ml of methanol. 10 g of sodium carbonate dissolved in30 ml of water were added to this mixture while stirring. Subsequently asolution of 8.2 g of iodine in 75 ml of methanol was added very slowly(in approximately 30 minutes). After stirring for 2 hours at roomtemperature the precipitate was filtered and washed with water tillneutral and subsequently washed with methanol. The reaction product waspurified by column chromatography using dichloromethane/ethylacetate(99:1) as eluent. ##STR506##

EXAMPLE 12 Synthesis of Dye I.106

1.3 g of dye I.129, 25 ml of acetone, 4.9 g of potassium carbonate and5.8 ml of benzylbromide were added together and were refluxed whilestirring for 8 hours. Potassium carbonate was filtered and the filtratewas concentrated under reduced pressure. The residual oil was purifiedby column chromatography. 1.1 g of dye I.106 was obtained.

EXAMPLE 13 Synthesis of Dye I.116

1 g of dye I.76 (prepared analogously to dye I.6) was dissolved in 5 mlof morpholine at 25° C. The solution was stirred for 30 minutes andthereafter poured into 40 ml of water. The precipitate was filtered,washed with water and purified by column chromatography (eluentdichloromethane/ethylacetate 95:5) to obtain 0.9 g of dye I.116.

EXAMPLE 14 Synthesis of Dye I.126

4.5 g of dye I.30, 60 ml of dichloromethane and 2.95 ml of pyridine wereadded together and 3.48 ml of ethylchloroformate were added dropwisehereto at 0° C. After 4 hours of stirring at room temperature thereaction mixture was diluted with 500 ml of ethylacetate. The mixturewas extracted with 500 ml of 0.1N hydrogen chloride, with water tillneutral and with 500 ml of saturated sodium chloride and dried overmagnesium sulfate. After filtration the solution was concentrated byevaporation to yield 3.8 g of dye I.126. After purification by columnchromatography (eluent dichloromethane) 1 g of pure dye I.126 wasobtained.

EXAMPLE 15 Synthesis of Dye I.127

5 g of dye I.32, 80 ml of dichloromethane, 160 ml of toluene, 17.7 ml oftriethylamine and 19.4 g of phthalic anhydride were added together andthe mixture was stirred for 24 hours at room temperature. The mixturewas thereafter left over-weekend in the refrigerator. The reactionmixture was diluted with 750 ml of ethylacetate. The mixture wasextracted six times with 500 ml of water and two times with 250 ml ofsaturated sodium chloride and dried over sodium sulfate. Afterfiltration the solution was concentrated by evaporation and dried undervacuum. After column chromatography 3 g of pure dye I.127 was obtained.

EXAMPLE 16 Synthesis of Dye I.128

5 g of dye I.32, 80 ml of dichloromethane, 160 ml of toluene, 17.7 ml oftriethylamine and 13.1 g of succinic anhydride were added together andthe mixture was left overnight at room temperature while stirring andwas thereafter left over-weekend in the refrigerator. The reactionmixture was diluted with 750 ml of ethylacetate. The mixture wasextracted six times with 500 ml of water and two times with 250 ml ofsaturated sodium chloride and dried over sodium sulfate. Afterfiltration the solution was concentrated by evaporation and dried undervacuum. 4.5 g of dye I.128 was obtained.

EXAMPLE 17 Synthesis of Dye I.129

2.0 g of dye I.61 were dissolved in 30 ml of dichloromethane. At 0° C.2.9 ml of triethylamine were added, followed by 2 ml ofethylchloroformate. The reaction mixture was stirred for 30 minutes atroom temperature. 250 ml of ethylacetate were added and subsequently themixture was washed with 1N hydrogen chloride (200 ml), water (3×500 ml)and brine (300 ml). The organic layer was dried over sodium sulfate,filtered and concentrated under reduced pressure to obtain 2.1 g of dyeI.129.

EXAMPLE 18 Synthesis of Dye II.11

2.3 g of dye II.23 was dissolved in 23 ml of dimethylsulfoxide and 0.31g of potassium cyanide was added. The reaction mixture was stirred for 1hour at room temperature. Subsequently 1.2 g of iodine were added. Thereaction mixture was poured out into water and extracted withdichloromethane. The organic phase was dried over sodium sulfate andconcentrated by evaporation. The reaction product was purified by columnchromatography. 0.65 g of dye II.134 was obtained.

EXAMPLE 19 Synthesis of Dye II.13

2 g of dye II.75, 80 ml of toluene and 40 ml of dichloromethane wereadded together while stirring. 1.3 g of triethylamine and 6.7 g ofsuccinic anhydride were added. The mixture was stirred for 24 hours.Thereafter the mixture was diluted with ethylacetate, washed with 1Nhydrogen chloride, with saturated sodium hydrogen carbonate and withsaturated sodium chloride and dried over sodium sulfate. The mixture wasconcentrated by evaporation and thereafter crystallized from ethanol.1.2 g of dye II.13 were obtained.

EXAMPLE 20 Synthesis of Dye II.15

2 g of dye II.75, 50 ml of dichloromethane and 7.25 ml of pyridine werestirred at 0° C. 9.5 g of ethylchloroformate were added dropwise. Themixture was stirred for 30 minutes. Thereafter the mixture was dilutedwith dichloromethane, washed twice with 1N hydrogen chloride, four timeswith saturated sodium chloride, once with saturated sodium hydrogencarbonate, twice with saturated sodium chloride. The organic phase wasdried over magnesium sulfate. The organic phase was concentrated byevaporation and thereafter crystallized from ethanol. 1.5 g of dye II.15were obtained.

EXAMPLE 21 Synthesis of Dye II.23

5 g of dye II.8 was dissolved in 100 ml of dichloromethane and 5.52 g ofmethyl succinic anhydride were added. At room temperature 7.76 g oftriethylamine were added slowly. The mixture was stirred for 15 minutes.The reaction product was purified by column chromatography usingdichloromethane as eluent. 5.5 g of dye II.23 were obtained.

EXAMPLE 22 Synthesis of Dye II.51

1 g of dye II.132 was dissolved in 10 ml of dimethylsulfoxide and 0.15 gof potassium cyanide was added hereto. The mixture was stirred for 20minutes at room temperature. Subsequently 0.6 g of iodine was added andthe mixture was stirred for another 20 minutes at room temperature. Themixture was poured out into 100 ml of dichloromethane and washed with asaturated sodium chloride solution. The organic phase was dried oversodium sulfate and concentrated by evaporation. The reaction product wasboiled in 20 ml of methanol, cooled and subjected to ultrasonictreatment for 5 minutes. The precipitate was filtered and washed withmethanol. 0.4 g of dye II.51 was obtained.

EXAMPLE 23 Synthesis of Dye II.75

5 g of 2,6-dimethyl-4H-pyran-4-one, 5.325 g of malononitrile dimer and50 ml of acetic anhydride were heated to 120° C. for 30 minutes. Themixture was left overnight. Thereafter the precipitate was filtered,washed with water and dried at 50° C. 7.3 g of dye II.75 were obtained.

EXAMPLE 24 Synthesis of Dye II.92

3 g of dye II.130 was dissolved in 50 ml of dichloromethane and 3.1 mlof pyridine. The reaction mixture was cooled and 3.6 ml ofethylchloroformate were added dropwise. The mixture was stirred at roomtemperature for 1 hour. Subsequently the reaction mixture was extractedwith ethylacetate and 1N hydrogen chloride, washed neutral, dried andconcentrated by evaporation. The reaction product was purified byrecrystallisation from ethanol.

EXAMPLE 25 Synthesis of Dye II.108

5 g of 2,6-diphenyl-4H-pyran-4-one, 2.7 g of malononitrile dimer and 50ml of acetic anhydride were heated to 120° C. while stirring. After 30minutes the mixture was cooled to room temperature. The precipitate wasfiltered, washed with water and methanol and dried at 50° C. Afterpurification by crystallization from ethanol 4.4 g of dye II.108 wereobtained.

EXAMPLE 26 Synthesis of Dye II.116

50 g of dye II.75 was dissolved in 500 ml of dichloromethane and stirredat room temperature. 109 ml of i-butylchloroformate were added slowly.The mixture was stirred at room temperature and 68 ml of dry pyridinewere added dropwise in approximately 15 minutes. The temperatureincreased to 42° C. After stirring for 30 minutes dichloromethane wasevaporated. The reaction product was recrystallized using 400 ml ofethanol and 200 ml of water and was left overnight in the refrigerator.The crystals were filtered, washed twice with a mixture of 50 ml ofwater and 75 ml of ethanol and twice with 125 ml of water, and dried at50° C. 62.6 g of dye II.116 were obtained.

EXAMPLE 27 Synthesis of Dye II.128

To 15 g of the below identified compound in 100 ml of ethanol was added8.76 g of malononitrile dimer. Three drops of piperidine were added andthe mixture was refluxed for 3 hours. The precipitate was filtered,washed with ethanol and dried. 18.7 g of dye II.128 was obtained.##STR507##

EXAMPLE 28 Synthesis of Dye II.130

10 g of the below identified compound, 6 g of malononitrile dimer, 60 mlof ethanol and 3 drops of piperidine were added together and wererefluxed for 4 hours. The mixture was left overnight to crystallize. Thecrystals were filtered, washed with ethanol and dried. 7.1 g of dyeII.130 was obtained. ##STR508##

EXAMPLE 29 Synthesis of Dye II.132

5 g of dye II.7 was dissolved in 125 ml of toluene and 40 ml ofdichloromethane. 19.2 ml of triethylamine and 10 g of phthalic anhydridewere added. The mixture was stirred at room temperature for 1 hour.Thereafter the mixture was diluted with ethylacetate and washed with a1N hydrogen chloride solution, water and a saturated sodium chloridesolution. The mixture was concentrated by evaporation and thereafterpurified by column chromatography using dichloromethane as eluent. 5.4 gof dye II.132 were obtained.

EXAMPLE 30 Synthesis of Dye III.8

3 g of malononitrile dimer and 20 ml of methanol were stirred at 0°-5°C. 5.3 g of p-diethylaminophenyl diazonium tetrafluorobromide saltdissolved in 20 ml of methanol was added dropwise. Thereafter 40 g ofice were added and a solution of 6 g of sodium acetate and 1 g of sodiumhydroxide in 100 ml of water was added dropwise. The mixture was stirredfor 1 h. The precipitate was filtered, washed with water and dried at50° C. 5.8 g of dye III.8 were obtained.

EXAMPLE 31 Synthesis of Dye IV.1

6 g of malononitrile dimer, 20 g of the below identified compound and400 ml of methanol were added together while stirring. ##STR509##

16 g of sodium carbonate dissolved in 100 ml of water was added dropwiseand thereafter a solution of 9.4 g iodine in 120 ml of methanol wasadded dropwise. The mixture was stirred for 30 minutes. The precipitatewas filtered, washed with water and dried at 50° C. Aftercrystallization from ethanol 8.7 g of dye IV.1 were obtained.

EXAMPLE 32 Synthesis of Dye IV.2

2 g of dye IV.1, together with 80 ml of toluene and 40 ml ofdichloromethane were stirred at room temperature. 0.8 g of triethylamineand 4.25 g of succinic anhydride were added. The mixture was left overweekend and then a further amount of 6 ml of triethylamine was added.The mixture was stirred overnight and was thereafter diluted withdichloromethane. The reaction product was washed with 1N hydrogenchloride, with water, with saturated sodium hydrogen carbonate and withsaturated sodium chloride. Then the reaction product was dried oversodium sulfate and concentrated by evaporation. After crystallizationfrom ethanol 1.6 g of dye IV.2 were obtained.

EXAMPLE 33 Synthesis of Dye IV.7

2 g of dye IV.1 were dissolved in 50 ml of dichloromethane and thesolution was stirred at 0° C. After adding 4.3 ml of pyridine, 5.76 g ofethylchloroformate was added dropwise. After stirring for 30 minutes afurther amount of 2.88 g of ethylchloroformate was added. Thereafter themixture was diluted with dichloromethane, washed twice with 1N hydrogenchloride, once with saturated sodium chloride, with saturated sodiumhydrogen carbonate and with saturated sodium chloride. The reactionproduct was dried over magnesium sulfate and concentrated byevaporation. After crystallization from ethanol 1.6 g of dye IV.7 wereobtained.

EXAMPLE 34 Synthesis of Dye IV.15

2.65 g of malononitrile dimer, 10 g of the below identified compound and175 ml of methanol were added together at room temperature whilestirring. ##STR510##

7 g of sodium carbonate dissolved in 45 ml of water was added dropwisewhile stirring and thereafter a solution of 4.25 g iodine in 55 ml ofmethanol was added dropwise. The mixture was stirred for 1 h. Theprecipitate was filtered, washed with methanol and water and dried at50° C. After crystallization from acetone 4 g of dye IV.15 wereobtained.

EXAMPLE 35 Synthesis of Dye IV.21

3 g of dye IV.15, 30 ml of dichloromethane and 9.5 ml of pyridine wereadded together and stirred on an ice bath. 178 ml of ethylchloroformatewas added dropwise. After stirring and check for completion of thereaction by thin layer chromatography (dichloromethane/methanol 98:2)the mixture was diluted with dichloromethane, washed with a 1N hydrogenchloride solution, with a saturated sodium chloride solution, dried overmagnesium sulfate and concentrated by evaporation. Afterrecrystallization from ethanol (80 ml) 2.4 g of dye IV.21 were obtained.

EXAMPLE 36 Synthesis of Dye IV.63

4 g of dye IV.57 (synthesized analogous to dye IV.15), 40 ml ofdichloromethane and 17 ml of pyridine were added together and stirred onan ice bath. 15.2 ml of ethylchloroformate was added dropwise. Afterstirring for 1 hour and check for completion of the reaction by thinlayer chromatography (dichloromethane/methanol 98:2) the mixture wasdiluted with ethyl acetate, washed with a 1N hydrogen chloride solution,with water, dried over magnesium sulfate and concentrated byevaporation. After recrystallization from ethanol (60 ml) 1.0 g of dyeIV.63 were obtained.

EXAMPLE 37 Synthesis of Dye V.15

13 g of malononitrile dimer, 27 g of the below identified compound and400 ml methanol were stirred. ##STR511##

32 g of sodium carbonate dissolved in 200 ml of water was added dropwiseand thereafter a solution of 38.5 g iodine in 430 ml of methanol wasadded dropwise. The mixture was stirred for 1 h. The precipitate wasfiltered, washed with methanol and water and dried. 19.2 g of dye V.15were obtained.

EXAMPLE 38

The absorption maxima (λ_(max)) and molar extinction coefficients (ε) ofthe dyes identified below were determined in methanol. The results arelisted in table 6.

                  TABLE 6                                                         ______________________________________                                        dye         λ.sub.max (nm)                                                                   ε(mol.sup.-1 cm.sup.-1 1)                       ______________________________________                                        I.6         638       82852                                                   I.8         611       67292                                                   I.13        534       55393                                                   I.16        620       74730                                                   I.19        610       52681                                                   I.20        625       68243                                                   I.22        638       57000                                                   I.25        537       43390                                                   I.26        526       47360                                                   I.28        638       86415                                                   I.31        533       43119                                                   I.35        604       48120                                                   I.36        638       83324                                                   I.37        653       83006                                                   I.42        526       38747                                                   I.46        537       34182                                                   I.49        521       28876                                                   I.51        515       39010                                                   I.52        655       76020                                                   I.61        523       46370                                                   I.62        538       45847                                                   I.64        419       34033                                                   I.65        614       67805                                                   I.70        525       30294                                                   I.76        624       66000                                                   I.77        614       63934                                                   I.82        505       28930                                                   I.85        527       47078                                                   I.91        628       64428                                                   I.92        637       82295                                                   I.93        638       80823                                                   I.94        638       89608                                                   I.95        638       89591                                                   I.96        638       91145                                                   I.97        552       42137                                                   I.103       584       34034                                                   I.106       602       60817                                                   I.107       638       85481                                                   I.108       535       54167                                                   I.109       620       75652                                                   I.111       638       80665                                                   I.114       591       46578                                                   I.115       629       25435                                                   I.116       515       43006                                                   I.117       639       106020                                                  I.121       515       42733                                                   I.122       531       51605                                                   I.124       623       62536                                                   I.125       610       81994                                                   I.126       626       67818                                                   I.127       617       31915                                                   I.128       635       57250                                                   I.134       638       91311                                                   I.136       642       65027                                                   I.138       638       63883                                                   I.140       527       47533                                                   I.141       534       57416                                                   I.142       638       94156                                                   II.4        388       28905                                                   II.5        551       68237                                                   II.6        434       36557                                                   II.7        431       27981                                                   II.9        484       40842                                                   II.11       644       31974                                                   II.13       457       28893                                                   II.15       451       34780                                                   II.17       340       18857                                                   II.22       453       28999                                                   II.23       573       70563                                                   II.24       340       23529                                                   II.26       547       73658                                                   II.27       452       27983                                                   II.30       405       36428                                                   II.34       525       18874                                                   II.35       643       23423                                                   II.39       500       46197                                                   II.45       548       56461                                                   II.51       620       34074                                                   II.52       525       10506                                                   II.59       523       39797                                                   II.61       529       38191                                                   II.63       345       18782                                                   Il.65       541       51855                                                   II.67       463       34925                                                   II.70       509       22013                                                   II.71       396       28132                                                   II.75       361       18818                                                   II.77       328       17010                                                   II.87       435       26971                                                   II.90       408       23311                                                   II.91       503       23117                                                   II.92       577       63729                                                   II.93       407       21138                                                   II.100      606       62890                                                   II.103      337       22699                                                   II.108      394       22645                                                   II.110      385                                                               II.111      362       21082                                                   II.112      451       42453                                                   II.113      419       34033                                                   II.115      452       29855                                                   II.116      453       31041                                                   II.117      421       19565                                                   II.118      454       30400                                                   II.123      457       27925                                                   II.124      484       32813                                                   II.127      569       26224                                                   II.128      458       23755                                                   II.129      443       30749                                                   II.130      460       33180                                                   II.131      477       35528                                                   II.132      549       52926                                                   II.133      551       48816                                                   III.8       250       43096                                                   III.9       247       33100                                                   IV.1        470       35187                                                   IV.2        543       55170                                                   IV.7        541       56566                                                   IV.21       513       32357                                                   IV.30       533       62454                                                   IV.63       579       55434                                                   V.1         437       25036                                                   ______________________________________                                    

EXAMPLE 39

A dye-donor element for use according to thermal dye sublimationtransfer was prepared as follows:

A solution of dye as identified in Table 7 and binder in 10 ml ofsolvent was prepared (the nature of the binder and the solvent isidentified below). From this solution a layer having a wet thickness of100 μm was coated on 6 μm thick polyethylene terephthalate film. Theresulting layer was dried by evaporation of the solvent.

A commercially available Hitachi material type VY S100A was used asreceiving element.

The dye-donor element was printed in combination with the receivingelement in a Hitachi color video printer VY-100A.

The receiver sheet was separated from the dye-donor element and themaximum color density of the recorded dye image on the receiving sheet(D_(max)) was measured by means of a Macbeth densitometer RD919 inStatus A mode.

The stability to light of the dyes was tested as follows. The receiversheet carrying transferred dye was divided into 3 strips. The firststrip was exposed for 5 hours, the second for 15 hours and the third for30 hours to white light and ultraviolet radiation in a Xenotest (tradename) type 50 apparatus of Hanau Quartzlampen GmbH, Hanau, W. Germany.The density was measured again and the loss of density in percent wasderived.

These experiments were repeated for each of the dye/binder combinationsidentified in table 7.

In table 7 B1 stands for co-vinylbutyral-vinylacetal-vinyl alcohol, B2for nitrocellulose with a nitrogen content between 6.75% and 14.4% byweight, B3 for cellulose acetate butyrate having an acetyl content of29.5% and a butyryl content of 17%, B4 for co-styrene-acrylonitrile, S1for methyl ethyl ketone, S2 for tetrahydrofuran, S3 for dichloromethane.

                  TABLE 7                                                         ______________________________________                                                mg dye/                 % density loss                                dye   binder  mg binder solvent                                                                             D.sub.max                                                                           5 h 15 h 30 h                             ______________________________________                                        I.6   B3      50/50     S1    230 (a)                                                                              3  10   16                               I.6   B2      50/20     S1    264    1   1    6                               I.8   B3      50/50     S1    133   15  42   73                               I.8   B2      50/20     S1    169   21  49   80                               I.13  B3      40/50     S1    198   86                                        I.13  B2      50/20     S1    219   89                                        I.16  B3      50/50     S1    263    9  22   61                               I.16  B3      50/50     S1    263    9  22   61                               I.16  B2      50/20     S1    262    2   8   23                               I.19  B3      50/50     S1    143    9  31   77                               I.19  B2      50/20     S1    173    5  31   76                               I.20  B3      50/50     S1    175   21  61                                    I.20  B2      50/20     S1    204   11  59                                    I.25  B3      50/50     S1    202   83                                        I.25  B2      50/20     S1    239   86                                        I.26  B3      50/50     S1    261    4  54   85                               I.26  B2      50/20     S1    239                                             I.26  B2      50/20     S1    239    4  54   85                               I.28  B3      50/50     S1    264    9  13   27                               I.28  B2      50/20     S1    234                                             I.28  B2      30/20     S1    258    3   9   24                               I.35  B3      50/50     S1    182   13  57                                    I.35  B2      50/20     S1    205    9  50                                    I.36  B3      50/50     S1    139    3  16   26                               I.36  B2      50/20     S1    241   38  25   37                               I.37  B3      50/50     S1    201   36  85                                    I.37  B2      50/20     S1    212   54  87                                    I.42  B2      50/50     S2    214   33  77                                    I.42  B2      50/20     S1    242   14  60                                    I.42  B2      50/20     S1    242   14  60                                    I.42  B2      50/50     S2    214   33  77                                    I.46  B3      50/50     S1    240   86                                        I.46  B2      50/20     S1    249   88                                        I.52  B3      50/50     S1    140   48                                        I.52  B2      50/20     S1    151   50                                        I.61  B4      50/50     S1    211   21  80   89                               I.62  B3      50/50     S1    223   90                                        I.62  B2      50/20     S1    251   90                                        I.65  B3      50/50     S1    205   41  63                                    I.65  B2      50/20     S1    239   54                                        I.70  B2      50/20     S1    222    3  62   92                               I.70  B3      50/50     S1    237   13  80   92                               I.76  B3      50/50     S1    257    6   9                                    I.76  B3      50/50     S1    257    2   7   12                               I.76  B2      50/20     S1    256    2   7   12                               I.76  B3      50/50     S1    198                                             I.76  B2      50/20     S1    190                                             I.77  B3      50/50     S1    203    2   3   51                               I.77  B2      50/20     S1    253   12  19   32                               I.85  B2      25/20     S1    269   18  79                                    I.85  B2      50/20     S1    262    8  53                                    I.85  B3      50/50     S1    275   10  70                                    I.91  B3      50/50     S1    211   17  52                                    I.91  B2      50/20     S1    213   14  63                                    I.92  B3      50/50     S1    237    8  23   60                               I.92  B2      50/20     S1    248    2   9   19                               I.93  B3      50/50     S1    197    8  19   68                               I.93  B2      50/20     S1    234    1   3   66                               I.94  B3      50/50     S1    225    4   5   13                               I.94  B2      50/20     S1    229    1   0    2                               I.95  B3      50/50     S1    233    4   9   17                               I.95  B2      50/20     S1    256    5   5    8                               I.96  B3      50/50     S1    229    9  28   58                               I.96  B2      50/20     S1    251    3   4   19                               I.106 B3      50/50     S1    225   74  90                                    I.106 B2      50/20     S1    244   68  91                                    I.106 B2      30/20     S1    189   70  89                                    I.107 B3      50/50     S1    177    1   2   24                               I.107 B2      50/20     SI    212    1   7   19                               I.108 B3      50/50     S1    223   17  56                                    I.108 B2      50/20     S1    229   16  54                                    I.109 B3      50/50     S1    227   14  94   78                               I.109 B2      50/20     S1    247    2  62   78                               I.111 B3      50/50     S1    181    2   3   12                               I.111 B2      50/20     S1    192    2   2    1                               I.115 B3      50/50     S1    196   30  81                                    I.115 B2      50/20     S1    222   54                                        I.116 B3      50/50     S1    236    3  22   55                               I.116 B2      50/20     S1    240    2  18   53                               I.117 B3      50/50     S1    208    5  12   25                               I.117 B2      50/20     S1    235    3   8   16                               I.121 B3      50/50     S1    261   15  47   71                               I.121 B2      50/20     S1    274   12  47   78                               I.121 B2      50/20     S1    274   12  47   78                               I.122 B2      50/20     S2    158   43  82                                    I.122 B2      50/20     S2    158   43                                        I.123 B4      40/50     S1    269   25  69                                    I.124 B3      50/50     S1    233    3  20   60                               I.124 B2      50/20     S1    198 (a)                                                                             10  23   61                               I.124 B3      50/50     S1    233    3  20   60                               I.125 B3      50/50     S1    199   10  33   64                               I.125 B2      50/20     S1    203   10  35   67                               I.126 B3      50/50     S1    254    7  35   68                               I.126 B2      50/20     S1    258   10  42   71                               I.127 B3      50/50     S1    151   26  61                                    I.127 B2      50/20     S1    176   23  61                                    I.128 B3      50/50     S1    270    2   9   45                               I.128 B2      50/20     S1    260    0   0    1                               I.134 B3      50/50     S1    260    2   5   10                               I.134 B2      50/20     S1    264    7   8   11                               I.136 B3      50/50     S1    189   12  14   47                               I.136 B2      50/20     S1    180   12  26   51                               I.138 B3      50/50     S1    208    6  19   26                               I.138 B2      50/20     S1    191    8  19   35                               I.140 B3      50/50     S1    198   89                                        I.140 B2      50/20     S1    203   89                                        I.141 B3      50/50     S1    150   57                                        I.141 B2      50/20     S1    192   28                                        I.142 B3      50/50     S1    182    0   1   23                               I.142 B2      50/20     S1    190    1   0    5                               II.5  B3      50/50     S1    177                                             II.5  B2      50/20     S1    270   72                                        II.7  B4      50/50     S1    238   57  87                                    II.7  B4      99/50     S1    248                                             II.7  B4      99/50     S1    196                                             II.9  B4      50/50     S1    235   90                                        II.13 B3      50/50     S1    188     7 12   19                               II.13 B2      50/20     S1    199    5  10   17                               II.15 B3      50/50     S1    205    5  10   14                               II.15 B2      50/20     S1    217    3   6   11                               II.22 B3      50/20     S1    144    3   4   10                               II.22 B2      50/20     S1    168    2   0    2                               II.22 B3      50/50     S1    158    0   2    7                               II.23 B3      50/50     S2    196   28  40   82                               II.23 B2      50/20     S2    239   23  64   85                               II.26 B3      50/50     S1    138   49                                        II.26 B2      50/20     S1    218   68                                        II.27 B2      50/20     S1    169   10  10   14                               II.27 B3      50/50     S1    125                                             II.34 B3      50/50     S1    145   93                                        II.34 B2      50/20     S1    166   94                                        II.35 B3      50/50     S1    136                                             II.35 B2      50/20     S1    187   83                                        II.45 B3      50/50     S1    236   88                                        lI.45 B2      50/20     S1    227   76                                        II.51 B3      50/50     S1    171   81                                        II.51 B2      50/20     S1    207   90                                        II.52 B3      50/50     S1    146   79                                        II.59 B3      50/50     S1    199   95                                        II.59 B2      50/20     S1    228   96                                        II.61 B3      50/50     S1    204   96                                        II.61 B2      50/20     S1    237   96                                        II.65 B3      50/50     S1    261   94                                        II.65 B2      50/20     S1    244   93                                        II.70 B2      50/20     S1    156   95                                        II.70 B3      50/50     S1    133   94                                        II.87 B3      50/50     S1    177   88                                        II.87 B2      50/20     S1    192   84                                        II.91 B3      50/50     S1    133   93                                        II.91 B2      50/20     S1    157   94                                        II.92 B3      50/50     S1    139   83                                        II.92 B2      50/20     S1    157   88                                        II.100                                                                              B3      50/50     S1    148   78                                        II.100                                                                              B2       50/200   S1    172   80                                        II.110                                                                              B2      100/20    S1    110   22  41   69                               II.110                                                                              B2      99/20     S1    110   22  41   69                               II.112                                                                              B2      50/20     S1    207   51  88                                    II.112                                                                              B2      50/20     S1    207   51  88                                    II.112                                                                              B4      50/50     S1    188                                             II.113                                                                              B3      50/50     S1    155   53  85                                    II.113                                                                              B3      50/50     S1    155   53  83                                    II.113                                                                              B2      50/20     S1    161    3  88                                    II.115                                                                              B3      50/50     S1    179    1   4    7                               II.115                                                                              B2      50/20     S1    196    3   2    5                               II.116                                                                              B2      50/20     S1    184    0   2    5                               II.116                                                                              B3      50/50     S1    165    2   7   11                               II.118                                                                              B3      50/50     S1    148    5    9  16                               II.118                                                                              B2      50/20     S1    148    2   5   12                               II.123                                                                              B3      50/50     S1    174    4   9   17                               II.123                                                                              B2      50/20     S1    194   13  14   21                               II.124                                                                              B2      50/20     S1    115    7  17   30                               II.127                                                                              B3      50/50     S1    115   86                                        II.127                                                                              B2      50/20     S1    132   87                                        II.128                                                                              B2      50/20     S1    117   82                                        II.129                                                                              B3      50/50     S1    131   82                                        II.129                                                                              B2      50/20     S1    151   83                                        II.130                                                                              B3      50/50     S1    125   83                                        II.130                                                                              B2      50/20     S1    134   84                                        II.131                                                                              B3      50/50     S1    133   91                                        II.131                                                                              B2      50/20     S1    159   92                                        II.132                                                                              B3      50/50     S1    200   79                                        II.132                                                                              B2      50/20     S1    209   79                                        II.133                                                                              B3      50/50     S1    232   62                                        II.133                                                                              B2      50/20     S1    239   62                                        III.9 B2      200/40    S1    134   13  10   20                               IV.1  B3      50/50     S2    141   30  74                                    IV.1  B2      50/20     S2    117   29  69                                    IV.2  B3      50/50     S2    115   23  69                                    IV.7  B3      50/50     S1    184   21  65   92                               IV.7  B2      50/20     S1    218   17  60   93                               IV.21 B3      50/50     S1    142   33  79                                    IV.21 B2      50/20     S1    230   23  76                                    V.15  B2/B3   50/50     S1    152                                             ______________________________________                                         (a) transmission density                                                 

I claim:
 1. Dye corresponding to the following formula ##STR512##wherein Z represents CN, COOR¹ or CONR² R³ ;R¹, R² and R³ eachindependently represents hydrogen, an alkyl group, a cycloalkyl group,an aryl group, or R² and R³ together represent the necessary atoms toclose a heterocyclic group; Y represents OR⁴ or NR⁵ R⁶ ; R⁴ representshydrogen, an alkyl group, a cycloalkyl group, an aryl group, SO₂ R⁷,COR⁷, CSR⁷, POR⁷ R⁸ ; R⁵ and R⁶ each independently has one of thesignificances given to R⁴ or represent an amino group, or R⁵ and R⁶together represent the necessary atoms to close a heterocyclic group,including a heterocyclic group with an aliphatic or aromatic ringfused-on, with the proviso that R⁵ and R⁶ do not both representhydrogen; R⁷ and R⁸ each independently represents an alkyl group, acycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, analkyloxy group, an aryloxy group, an alkylthio group, an arylthio group,an amino group or a heterocyclic group or R⁷ and R⁸ together representthe necessary atoms to close a 5- or 6-membered ring; R¹⁵, R¹⁶, R¹⁸ andR¹⁹ each independently represents hydrogen, an alkyl group, a cycloalkylgroup, an aryl group, an alkyloxy group, an aryloxy group, a carbonamidogroup, a sulfamido group, hydroxy, halogen, NH-SO₂ R⁷, NH-COR⁷, O-SO₂R⁷, O-COR⁷, or R¹⁵ and R¹⁶ together and/or R¹⁸ and R¹⁹ togetherrepresent the necessary atoms to close (a) ring(s) fused-on the benzenering or R¹⁶ and/or R¹⁸ together with R²¹ and/or R²² represent thenecessary atoms to close a heterocyclic ring fused-on the benzene ring;R¹⁷ represents OR²⁰, SR²⁰ or NR²¹ R²² ; R²⁰ represents hydrogen, analkyl group, a cycloalkyl group, an aryl group, and R²¹ and R²² eachindependently has one of the significances given to R²⁰ or represent aheterocyclic group or R²¹ and R²² together represent the necessary atomsto close a heterocyclic ring or R²¹ and/or R²² together with R¹⁶ and/orR¹⁸ represent the necessary atoms to close a heterocyclic ring fused-onthe benzene ring.